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WO2018047695A1 - Composition containing perfluoro(poly)ether group-containing silane compound - Google Patents

Composition containing perfluoro(poly)ether group-containing silane compound Download PDF

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Publication number
WO2018047695A1
WO2018047695A1 PCT/JP2017/031171 JP2017031171W WO2018047695A1 WO 2018047695 A1 WO2018047695 A1 WO 2018047695A1 JP 2017031171 W JP2017031171 W JP 2017031171W WO 2018047695 A1 WO2018047695 A1 WO 2018047695A1
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Prior art keywords
group
independently
integer
ocf
occurrence
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PCT/JP2017/031171
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French (fr)
Japanese (ja)
Inventor
尚志 三橋
孝史 野村
雅聡 能勢
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ダイキン工業株式会社
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=61562334&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2018047695(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by ダイキン工業株式会社 filed Critical ダイキン工業株式会社
Priority to KR1020197004826A priority Critical patent/KR102322019B1/en
Priority to JP2018538375A priority patent/JP6724994B2/en
Priority to KR1020217035478A priority patent/KR20210136148A/en
Priority to CN201780054313.7A priority patent/CN109689786A/en
Publication of WO2018047695A1 publication Critical patent/WO2018047695A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
    • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
    • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to a composition comprising a perfluoro (poly) ether group-containing silane compound, specifically a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative.
  • a composition comprising a perfluoro (poly) ether group-containing silane compound, specifically a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative.
  • fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate.
  • a layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. ing.
  • a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. It has been.
  • Patent Documents 1 and 2 describe a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part.
  • a layer obtained from a surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit functions such as water repellency, oil repellency, and antifouling properties even in a thin film, and thus glasses that require light transmission and transparency are required. It is suitably used for optical members such as touch panels. In particular, in these applications, friction durability is required so that such a function can be maintained even after repeated friction.
  • the present invention relates to a composition
  • a composition comprising a perfluoro (poly) ether group-containing silane compound capable of forming a layer having water repellency, oil repellency, antifouling property, waterproof property and high friction durability.
  • the purpose is to provide goods.
  • the present inventors have found that high friction durability can be obtained by using a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative.
  • the present inventors have found that a surface treatment layer can be formed and have completed the present invention.
  • PFPE 1 has the formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of existence of each repeating unit with a, b, c, d, e or f and parenthesized is arbitrary in the formula.)
  • Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more
  • an article comprising a substrate and a layer formed from the composition of the present invention on the surface of the substrate.
  • each Rf 2 independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
  • Each of PFPE 2 is independently-(OC 6 F 12 ) a- (OC 5 F 10 ) b- (OC 4 F 8 ) c- (OC 3 F 6 ) d- (OC 2 F 4 ) e- (OCF 2)
  • f - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f Is at least 1, and the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula;
  • Z 2 represents a single bond or a divalent organic group;
  • x is 1 or 2; when x is 1, A is —COOR 3 , —PO (OR
  • a surface treatment layer having high friction durability is formed by using a composition containing the perfluoro (poly) ether group-containing silane compound of the present invention and a perfluoro (poly) ether group-containing acid or acid derivative. Can do.
  • hydrocarbon group means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon.
  • Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned.
  • the “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated.
  • the hydrocarbon group may also contain one or more ring structures.
  • Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
  • the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
  • divalent to decavalent organic group means a divalent to decavalent group containing carbon.
  • a divalent to decavalent organic group is not particularly limited, and examples thereof include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group.
  • the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is further eliminated from a hydrocarbon group.
  • the present invention includes the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2): At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formula (E1): At least one perfluoro (poly) ether group-containing acid or acid derivative (hereinafter also referred to as “perfluoro (poly) ether-modified compound”) (Hereinafter also referred to as “the composition of the present invention”).
  • perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) explain.
  • each PFPE 1 is independently - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - It is group represented by these.
  • a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
  • the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
  • repeating units may be linear or branched, but are preferably linear.
  • -(OC 6 F 12 )- is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — — (OCF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred.
  • -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
  • — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
  • the PFPE 1 is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
  • PFPE 1 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • PFPE 1 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
  • PFPE 1 is, - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - ( wherein, c and d, respectively Each independently represents an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts c, d, The order of presence of each repeating unit in parentheses attached with e or f is arbitrary in the formula).
  • PFPE 1 is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —.
  • PFPE 1 is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more Preferably, it is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit with the subscript e or f and enclosed in parentheses is arbitrary in the formula).
  • PFPE 1 is a group represented by — (R 6 —R 7 ) q —.
  • R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups.
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups is there.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • Q is an integer of 2 to 100, preferably an integer of 2 to 50.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear.
  • PFPE 1 is preferably — (OC 2 F 4 —OC 3 F 6 ) q — or — (OC 2 F 4 —OC 4 F 8 ) q —.
  • Rf 1 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • Rf 1 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group, A perfluoroalkyl group having 1 to 16 carbon atoms is preferred.
  • the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
  • R 1 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
  • hydrolyzable group as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction.
  • hydrolyzable group examples include —OR, —OCOR, —O—N ⁇ CR 2 , —NR 2 , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, and —OR (that is, an alkoxy group) is preferable.
  • R examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • R 11 independently represents a hydrogen atom or a halogen atom at each occurrence.
  • the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
  • R 12 each independently represents a hydrogen atom or a lower alkyl group.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • n1 is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 1 n1 R 2 3-n1 ) unit. However, in the formula, all n1 are not 0 at the same time. In other words, at least one R 1 is present in the formula.
  • each X 1 independently represents a single bond or a divalent to 10-valent organic group.
  • X 1 is a perfluoropolyether moiety (ie, Rf 1 -PFPE 1 part or -PFPE 1 which mainly provides water repellency, surface slipperiness, etc.) in the compounds represented by formulas (A1) and (A2).
  • -Part a perfluoropolyether moiety
  • silane part ie, a group enclosed in parentheses with ⁇
  • X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • These ⁇ and ⁇ ′ can vary depending on the valence of X 1 .
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X 1 .
  • X 1 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ 'Can be nine.
  • ⁇ and ⁇ ′ are 1.
  • alpha is a value obtained by subtracting 1 from the valence of X 1.
  • X 1 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
  • X 1 is a divalent to tetravalent organic group
  • ⁇ is 1 to 3
  • ⁇ ′ is 1.
  • X 1 is a divalent organic group
  • ⁇ is 1
  • ⁇ ′ is 1.
  • the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
  • Examples of X 1 are not particularly limited, but for example, the following formula: -(R 31 ) p ' -(X a ) q'- [Where: R 31 each independently represents a single bond, — (CH 2 ) s ′ — or o-, m- or p-phenylene group, preferably — (CH 2 ) s ′ — s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
  • X a represents-(X b ) l ' - X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 —, —O—CONR 34 —, —NR 34 — and — (CH 2 ) n ′ —
  • R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, and more preferably a methyl group.
  • R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
  • m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
  • n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
  • R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group It may be substituted with a substituent.
  • X 1 is — (R 31 ) p ′ — (X a ) q ′ —R 32 —.
  • R 32 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —.
  • t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
  • R 32 (typically a hydrogen atom of R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
  • X 1 is Single bond, A C 1-20 alkylene group, -R 31 -X c -R 32- , or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
  • said X 1 is Single bond, A C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- , or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above]. ] It is.
  • X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- , —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (R 33 ) 2 —O—Si (R 33 ) 2 —CH 2 CH 2 —Si (R 33 ) 2 —O—Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —, —CONR 34 — (CH 2 ) u ′ — (Si (Si (OC
  • X d is -S-, -C (O) O-, -CONR 34 -, —CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 — [Wherein each symbol is as defined above. ] Represents.
  • said X 1 is Single bond, A C 1-20 alkylene group, — (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ — [Wherein each symbol is as defined above. ] It can be.
  • said X 1 is Single bond, A C 1-20 alkylene group, — (CH 2 ) s ′ —O— (CH 2 ) t ′ —, - (CH 2) s' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, — (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s′— O— (CH 2 ) t ′ —Si (R 33 ) 2 — (CH 2 ) u ′ —Si (R 33 ) 2 — (C v H 2v ) —
  • R 33 , m ′, s ′, t ′ and u ′ are as defined above, and
  • — (C v H 2v ) — may be linear or branched.
  • the X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). May be.
  • examples of X 1 groups include the following groups: [Wherein, each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; D is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CF 2 O (CH 2 ) 3 —, -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), and (In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more
  • X 1 include, for example: Single bond, —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 )
  • X 1 is a group represented by the formula: — (R 16 ) x — (CFR 17 ) y — (CH 2 ) z —.
  • x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is Is optional.
  • R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 26 — (wherein R 26 represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there.
  • R 16 is an oxygen atom or a divalent polar group.
  • the “divalent polar group” is not particularly limited, but —C (O) —, —C ( ⁇ NR 27 ) —, and —C (O) NR 27 — (in these formulas, R 27 is Represents a hydrogen atom or a lower alkyl group).
  • the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.
  • R 17 is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence.
  • the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.
  • X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above
  • x, y and z are as defined above
  • the order in which each repeating unit is included is arbitrary in the formula).
  • Examples of the group represented by the above formula: — (O) x — (CF 2 ) y — (CH 2 ) z — include, for example, — (O) x ′ — (CH 2 ) z ′′ —O — [(CH 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′′ ′′ (wherein x ′ is 0 or 1, y ′′, z ′′ and z ′ ′′ are each independently an integer of 1 to 10, and z ′′ ′′ is 0 or 1) These groups are bonded at the left end to the PFPE 1 side.
  • X 1 is —O—CFR 13 — (CF 2 ) g —.
  • Each R 13 independently represents a fluorine atom or a lower fluoroalkyl group.
  • the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
  • the above g is independently 0 or 1.
  • R 13 is a fluorine atom and e is 1.
  • X 1 is a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 .
  • —X c —CO—NR 14 —X d — is a divalent group
  • —X c —CO—N (—X d —) 2 is a trivalent group.
  • R 14 represents a hydrogen atom, a lower alkyl group or a phenyl group.
  • the lower alkyl group may be preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a methyl group.
  • Xc represents a single bond or a divalent organic group.
  • the divalent organic group in Xc is preferably, -(CR 8 2 ) k1- (O) k2- (NR 9 ) k3- [Where: Each R 8 is independently a hydrogen atom or a fluorine atom; Each R 9 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group; k1 is an integer from 1 to 20; k2 is an integer from 0 to 10; k3 is an integer from 0 to 10; Here, k 1, k 2 or k 3 is attached in parentheses, and the order of existence of each repeating unit is arbitrary in the formula. ] It can be group represented by these.
  • Xd represents a divalent organic group.
  • the divalent organic group in X d is preferably - (CR 20 2) k4 - (O) k5 - (NR 21) k6 -, [Where: Each R 20 is independently a hydrogen atom or a fluorine atom; Each R 21 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group; k4 is an integer from 1 to 20; k5 is an integer from 0 to 10; k6 is an integer from 0 to 10; Here, k4, k5 or k6 is added in parentheses, and the order of existence of each repeating unit is arbitrary in the formula. ] It can be group represented by these.
  • X c is — (CF 2 ) k1 ′ — or — (CF 2 ) k1 ′ — (O) k2 ′ —.
  • k1 ′ is an integer from 1 to 6
  • k2 ′ is an integer from 1 to 3
  • k1 ′ or k2 ′ is added in parentheses, and the order of existence of each repeating unit is arbitrary in the formula.
  • X d represents — (CH 2 ) k4 ′ — or — (CH 2 ) k4 ′ —O k5 ′ —.
  • k4 ′ is an integer from 1 to 6; k5 ′ is an integer from 1 to 3; Here, k4 ′ or k5 ′ is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ] It is.
  • examples of X 1 groups include the following groups: [Where: Each of R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group; In each X 1 group, any some of T are bound to the PFPE 1 of the molecular backbone: —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CF 2 O (CH 2 ) 3 —, -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), or [Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a
  • T are groups opposite to PFPE 1 of the molecular backbone (ie, formula (A1), — (CH 2 ) n bonded to a carbon atom in (A2), (D1) and (D2), and to a Si atom in the following formulas (B1), (B2), (C1) and (C2)) “ — (N” is an integer of 2 to 6), and when present, the remainder can each independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, a radical scavenging group or an ultraviolet absorbing group. .
  • the radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation.
  • benzophenones benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates , Hindered amines, hindered phenols, or triazine residues.
  • the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays.
  • benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
  • preferred radical scavenging groups or ultraviolet absorbing groups include Is mentioned.
  • X 1 can be each independently a trivalent to 10 valent organic group.
  • t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.
  • X 2 independently represents a single bond or a divalent organic group at each occurrence.
  • X 2 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably, - (CH 2) u - (wherein, u is an integer of 0 to 2) a.
  • Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′): [Where: Each PFPE 1 is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.) A group represented by: Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; R 1 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R 2 independently represents a hydrogen atom or an al
  • the compounds represented by the above formulas (A1) and (A2) can be prepared by, for example, using perfluoropolyether derivative corresponding to Rf 1 -PFPE 1 -moiety as a raw material, introducing iodine at the terminal, and then —CH 2 CR 12 It can be obtained by reacting a vinyl monomer corresponding to (X 2 —SiR 1 n1 R 2 3-n1 ) —.
  • Rf 1 , PFPE 1 , R 1 , R 2 and n1 are the same as those described for the above formulas (A1) and (A2).
  • X 5 each independently represents a single bond or a divalent to 10-valent organic group.
  • the X 5 is a perfluoropolyether part (Rf 1 -PFPE 1 part or -PFPE 1 -part) which mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (B1) and (B2).
  • a silane moiety specifically, —SiR 1 n1 R 2 3-n1 ) that provides the binding ability to the base material. Therefore, X 5 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • ⁇ and ⁇ ′ are determined according to the valence of X 3
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X 5 .
  • X 5 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ 'Can be nine.
  • ⁇ and ⁇ ′ are 1.
  • beta is a value obtained by subtracting 1 from the valence of the value of X 5.
  • X 5 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
  • X 5 is a divalent to tetravalent organic group
  • ⁇ is 1 to 3
  • ⁇ ′ is 1.
  • X 5 is a divalent organic group
  • ⁇ is 1
  • ⁇ ′ is 1.
  • the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
  • Examples of X 5 are not particularly limited, and examples thereof include those similar to those described for X 1 .
  • X 5 may be a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 .
  • X c , X d and R 14 are in the same positions as described for X 1 above.
  • Preferred specific X 5 is Single bond, —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2
  • Preferred compounds represented by formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′): [Where: Each PFPE 1 is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.) A group represented by: Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; R 1 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group; R 2 independently represents a hydrogen atom or an al
  • the compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in Patent Document 1 or an improved method thereof.
  • the compounds represented by the formulas (B1) and (B2) are represented by the following formulas (B1-4) or (B2-4): [Where: Each PFPE 1 is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
  • a group represented by: Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine
  • HSiM 3 (wherein, M is independently a halogen atom, R 1 or R 2 , and R 1 is independently a hydroxyl group or hydrolyzable at each occurrence)
  • R 2 is independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence, and the halogen atom is optionally substituted with R 1 or R 2.
  • PFPE 1 , Rf 1 , X 5 ′ , ⁇ , ⁇ ′ and R 92 are as defined above; n1 is an integer of 0 to 3. ] It can obtain as a compound represented by these.
  • Rf 1 and PFPE 1 are the same as those described for the above formulas (A1) and (A2).
  • X 7 each independently represents a single bond or a divalent to 10-valent organic group.
  • the X 7 is a perfluoropolyether part (Rf 1 -PFPE 1 part or -PFPE 1 -part) which mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (C1) and (C2).
  • a silane moiety specifically, —SiR a k1 R b 11 R c m1 group
  • X 7 may be any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • ⁇ and ⁇ ′ are determined according to the valence of X 7
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X 7 .
  • X 7 is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ .
  • gamma is a value obtained by subtracting 1 from the valence of the values of X 7.
  • X 7 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
  • X 7 is a divalent to tetravalent organic group, ⁇ is 1 to 3, and ⁇ ′ is 1.
  • X 7 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
  • the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
  • Examples of X 7 are not particularly limited, and examples thereof include those similar to those described for X 1 .
  • X 5 may be a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 .
  • X c and X d are the same positions as described for X 1 above.
  • Preferred specific X 7 is Single bond, —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2
  • R a independently represents —Z 1 —SiR 71 p1 R 72 q1 R 73 r1 at each occurrence.
  • Z 1 represents an oxygen atom or a divalent organic group independently at each occurrence.
  • Z 1 is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which R a is bonded) at the end of the molecular main chain in formula (C1) or formula (C2). Does not include what to do.
  • Z 1 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 1 to 6, and h is 1 to 6 is an integer of 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group.
  • These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • R 71 represents R a ′ independently at each occurrence.
  • R a ′ has the same meaning as R a .
  • the maximum number of Si linked in a straight chain via the Z 1 group is 5. That is, in the above R a , when at least one R 71 is present, there are two or more Si atoms linearly linked through the Z 1 group in R a. The maximum number of Si atoms connected in a straight line is five.
  • the "number of Si atoms linearly linked via a Z group in R a" is equal to -Z 1 -Si- repetition rate of which is connected to a linear during R a .
  • Z Z 1 group
  • * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition.
  • the number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *.
  • the chain in which ZSi repetition is completed in Si 2 has “the number of Si atoms linearly linked through Z 1 group in R a ”, and similarly, Si 3 , Si
  • the chains in which the ZSi repetition is terminated with 4 and Si 5 have “number of Si atoms connected in a straight chain via the Z 1 group in R a ” being 3, 4 and 5, respectively.
  • the number of Si atoms connected linearly via the Z 1 group in R a is 1 (left formula) or 2 ( (Right type).
  • the number of Si atoms connected in a straight chain via a Z group in R a is 1 or 2, preferably 1.
  • R 72 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction.
  • hydrolyzable groups include —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group).
  • R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R 72 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • R 73 independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the terminal portions of R a is —Si (—Z 1 —SiR 72 q R 73 r ) 2 or —Si (—Z 1 —SiR 72 q R 73 r ) 3 , preferably — Si (—Z 1 —SiR 72 q R 73 r ) 3
  • - the unit of (Z 1 -SiR 72 q R 73 r) is preferably (-Z 1 -SiR 72 3).
  • the terminal portions of R a may be all —Si (—Z 1 —SiR 72 q R 73 r ) 3 , preferably —Si (—Z 1 —SiR 72 3 ) 3 .
  • R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
  • R b is preferably a hydroxyl group, —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is substituted or unsubstituted)
  • An alkyl group having 1 to 4 carbon atoms preferably —OR.
  • R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group. More preferably, R c is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
  • R c independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • the compounds represented by the above formulas (C1) and (C2) are, for example, using a perfluoropolyether derivative corresponding to the Rf 1 -PFPE 1 -moiety as a raw material, introducing a hydroxyl group at the terminal, and then unsaturated bond at the terminal
  • a group having an unsaturated bond, a group having an unsaturated bond and a silyl derivative having a halogen atom are reacted, a hydroxyl group is further introduced into the terminal of the silyl group, and the group having an unsaturated bond and the silyl derivative are introduced.
  • Preferred compounds represented by the formulas (C1) and (C2) are represented by the following formulas (C1 ′′) and (C2 ′′): [Where: Each PFPE 1 is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.) A group represented by: Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms; X 7 represents —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2
  • each PFPE 1 is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
  • a group represented by: Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
  • Each X 7 ′ independently represents a single bond or a divalent to 10-valent organic group; each ⁇ is independently an integer from 1 to 9;
  • the obtained compound represented by the formula (C1-6) or (C2-6) is converted into HSiM 3 (wherein M is independently a halogen atom, R 72 or R 73 , and R 72 is Each independently at each occurrence represents a hydroxyl group or a hydrolyzable group, and R 73 each independently at each occurrence represents a hydrogen atom or a lower alkyl group.)
  • the halogen atom is converted to R 72 or R 73 to give the formula (C1 ′ ′′) or (C2 ′ ′′):
  • Rf 1 , PFPE 1 , R 72 , R 73 , R 92 , R 94 , R b , R c , ⁇ , ⁇ ′, X 7 ′ , k1, l1 and m1 are as defined above.
  • q1 is independently an integer of 1 to 3 at each occurrence
  • r1 is an integer of 0 to 2 independently at each occurrence.
  • Rf 1 and PFPE 1 are the same as those described for the above formulas (A1) and (A2).
  • X 9 each independently represents a single bond or a divalent to 10-valent organic group.
  • X represents a perfluoropolyether moiety (ie, Rf 1 -PFPE 1 part or -PFPE 1- Part) and a part that provides the binding ability to the substrate (that is, a group attached with ⁇ and enclosed in parentheses). Therefore, X may be any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.
  • ⁇ is an integer of 1 to 9
  • ⁇ ′ is an integer of 1 to 9.
  • ⁇ and ⁇ ′ can vary depending on the valence of X.
  • the sum of ⁇ and ⁇ ′ is the same as the valence of X.
  • X is a 10-valent organic group
  • the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ ′.
  • X 9 is a divalent organic group
  • ⁇ and ⁇ ′ are 1.
  • [delta] is a value obtained by subtracting 1 from the valence of X 9.
  • X 9 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
  • X 9 is a divalent to tetravalent organic group, ⁇ is 1 to 3, and ⁇ ′ is 1.
  • X 9 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
  • the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
  • Examples of X 9 are not particularly limited, and examples thereof include those similar to those described with respect to X 1 .
  • X 5 may be a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 .
  • X c and X d are the same positions as described for X 1 above.
  • Preferred specific X 9 is Single bond, —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2
  • R d independently represents —Z 2 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
  • Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence.
  • Z 2 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH 2 ) i- (where i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • R 81 independently represents R d ′ at each occurrence.
  • R d ′ has the same meaning as R d .
  • R d the maximum number of C linked in a straight chain via the Z 2 group is 5. That is, in the above R d , when at least one R 81 is present, there are two or more C atoms linearly linked through the Z 2 group in the R d , but through the Z 2 group, The maximum number of C atoms connected in a straight line is five.
  • the phrase "through the Z 2 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 -C- being linearly linked in a R d Become. This is the same as the description regarding R a in the formulas (C1) and (C2).
  • the “number of C atoms connected in a straight chain via a Z 2 group in R d ” is 1 (left formula) or 2 (right formula) in all chains.
  • the number of C atoms linked in a straight chain via a Z 2 group in R d is 1 or 2, preferably 1.
  • R 82 represents —Y—SiR 85 n2 R 86 3-2n .
  • Y represents a divalent organic group independently at each occurrence.
  • Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 Is an integer, h ′ is an integer from 0 to 6, for example, an integer from 1 to 6, or —phenylene- (CH 2 ) i ′ — (where i ′ is an integer from 0 to 6) ).
  • These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
  • Y can be a C 1-6 alkylene group, —O— (CH 2 ) h ′ — or —phenylene- (CH 2 ) i ′ —.
  • Y is a group as described above, light resistance, particularly ultraviolet light resistance can be further increased.
  • R 5 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
  • hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction.
  • hydrolyzable groups include —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group).
  • R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
  • an alkyl group particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
  • the hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
  • R 85 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).
  • R 86 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • n2 independently represents an integer of 1 to 3, preferably 2 or 3, more preferably 3, for each (-Y-SiR 85 n2 R 86 3-n2 ) unit.
  • R 83 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p2, q2 and r2 is 3.
  • '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
  • At least one of the terminal ends of R d is —C (—Y—SiR 85 q2 R 86 r2 ) 2 or —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C ( may be -Y-SiR 85 q2 R 86 r2 ) 3.
  • (- Y-SiR 85 q2 R 86 r2) units is preferably (-Y-SiR 85 3).
  • the terminal portions of R d may be all —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C (—Y—SiR 85 3 ) 3 .
  • R e independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence.
  • Y, R 85 , R 86 and n2 are as defined in R 82 above.
  • R f independently represents a hydrogen atom or a lower alkyl group at each occurrence.
  • the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
  • k2 is independently an integer of 0 to 3 at each occurrence; l2 is independently an integer of 0 to 3 at each occurrence; and m2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of k2, l2, and m2 is 3.
  • At least one k2 is 2 or 3, preferably 3.
  • k2 is 2 or 3, preferably 3.
  • l2 is 2 or 3, preferably 3.
  • At least one q2 is 2 or 3, or at least one l is 2 or 3. That is, there are at least two —Y—SiR 85 n2 R 86 3-n2 groups in the formula.
  • the perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods.
  • the compound represented by the formula (D1 ′) in which X is divalent is not limited, but can be produced as follows.
  • a group containing a double bond preferably a polyhydric alcohol represented by HO—X—C (YOH) 3 (wherein X and Y are each independently a divalent organic group)) Is allyl), and halogen (preferably bromo), and Hal—X—C (Y—O—R—CH ⁇ CH 2 ) 3 (where Hal is halogen, eg Br, R is A double bond-containing halide represented by a valent organic group such as an alkylene group.
  • R PFPE —OH a perfluoropolyether group-containing alcohol represented by R PFPE —OH (wherein R PFPE is a perfluoropolyether group-containing group), and R PFPE ⁇ O—X—C (Y—O—R—CH ⁇ CH 2 ) 3 is obtained.
  • the terminal —CH ⁇ CH 2 is then reacted with HSiCl 3 and alcohol or HSiR 85 3 to give R PFPE —O—X—C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ) 3 Can be obtained.
  • the perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 .
  • the number average molecular weight is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and still more preferably 3,000 to 8,000.
  • the “number average molecular weight” is measured by 19 F-NMR.
  • PFPE 2 is a perfluoro (poly) ether group similar to PFPE 1 described above, and each independently represents a formula: - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - It is group represented by these.
  • a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1.
  • a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less.
  • the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
  • the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
  • repeating units may be linear or branched, but are preferably linear.
  • -(OC 6 F 12 )- is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — — (OCF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred.
  • -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
  • — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
  • the PFPE 2 is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
  • PFPE 2 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
  • PFPE 2 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
  • PFPE 2 is-(OC 4 F 8 ) c- (OC 3 F 6 ) d- (OC 2 F 4 ) e- (OCF 2 ) f-where c and d are each Each independently represents an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts c, d, The order of presence of each repeating unit in parentheses attached with e or f is arbitrary in the formula).
  • PFPE 2 is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —.
  • PFPE 2 is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently from 1 to 200, preferably from 5 to 200, Preferably, it is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit with the subscript e or f and enclosed in parentheses is arbitrary in the formula).
  • PFPE 2 is a group represented by — (R 6 —R 7 ) q —.
  • R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 .
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups.
  • R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups is there.
  • the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
  • Q is an integer of 2 to 100, preferably an integer of 2 to 50.
  • OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear.
  • PFPE 2 is preferably — (OC 2 F 4 —OC 3 F 6 ) q — or — (OC 2 F 4 —OC 4 F 8 ) q —.
  • Rf 2 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
  • alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
  • Rf 2 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group, A perfluoroalkyl group having 1 to 16 carbon atoms is preferred.
  • the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
  • Z 2 represents a single bond or a divalent organic group.
  • the divalent organic group in Z 2 is preferably -(CR 18 2 ) k7- (O) k8- (NR 19 ) k9- , [Where: Each R 18 is independently a hydrogen atom or a fluorine atom; R 19 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group; k7 is an integer from 1 to 20; k8 is an integer from 0 to 10; k9 is an integer from 0 to 10; Here, k7, k8 or k9 is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ] It is.
  • Preferred Z 2 is -(CF 2 ) k7 ' -or-(CF 2 ) k7' -(O) k8 ' - [Where: k7 ′ is an integer from 1 to 6; k8 ′ is an integer from 1 to 3; Here, k7 ′ or k8 ′ is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ] It is.
  • x is 1 or 2, and when x is 1, A is —COOR 3 , —PO (OR 3 ) 2 , —SO 2 (OR 3 ), or —SO (OR 3 ). Yes, when x is 2, A is —PO (OR 3 ) —. When x is 2, the two Rf 2 -PFPE 2 may be the same or different.
  • R 3 is a hydrogen atom or a hydrocarbon group.
  • the hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
  • x is 1 and A is —COOR 3 .
  • x is 1 and A is —COOH.
  • x is 1 and A is —COOCH 3 .
  • the perfluoro (poly) ether-modified compound represented by the above formula (E1) may be an unreacted raw material compound when synthesizing the perfluoro (poly) ether group-containing silane compound, or may be added separately. It may be a compound. The compound added separately may be the same compound as the compound used for the synthesis, or may be a different compound.
  • the perfluoro (poly) ether-modified compound represented by the above formula (E1) is not particularly limited, but may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 .
  • the number average molecular weight is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and still more preferably 3,000 to 8,000.
  • the perfluoro (poly) ether group-containing silane represented by the above formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The difference between the number average molecular weight of the compound and the number average molecular weight of the perfluoro (poly) ether-modified compound represented by the formula (E1) is within 2,000, preferably within 1,500, more preferably within 1,000. More preferably, it is within 500.
  • the content ratio of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether-modified compound is 99.99: 0.01 to 70:30, preferably 99. .5: 0.5 to 80:20, more preferably 99: 1 to 90:10.
  • the perfluoro (poly) ether modified compound can efficiently catalyze the reaction between the perfluoro (poly) ether group-containing silane compound and the substrate.
  • the ratio of the content of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether-modified compound in the composition of the present invention is 99.99: 0.01 to 97: 3, preferably 99.9: 0.1 to 98: 2. In another embodiment, the ratio of the content of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether-modified compound in the composition of the present invention is 95: 5 to 70:30, preferably 92: 8 to 80:20.
  • composition of the present invention may contain other components in addition to the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound.
  • other components are not particularly limited.
  • other surface treatment compounds (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers.
  • fluorinated oil a compound that can be understood as a silicone oil (hereinafter referred to as “silicone oil”) that can be understood as a silicone oil (hereinafter referred to as “silicone oil”)
  • a catalyst and the like.
  • Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms
  • Rf 6 represents Represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom
  • Rf 5 and Rf 6 Are more preferably each independently a C 1-3 perfluoroalkyl group.
  • a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300.
  • the order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula.
  • — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —.
  • — (OCF 2 CF 2 ) — is preferable.
  • — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
  • perfluoro (poly) ether compound represented by the general formula (3) a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds) may be used. May be included).
  • Rf 5 and Rf 6 are as described above; in formula (3a), b ′′ is an integer of 1 to 100; in formula (3b), a ′′ and b ′′ are Each independently represents an integer of 1 to 30, and c ′′ and d ′′ are each independently an integer of 1 to 300.
  • the order of existence of each repeating unit with subscripts a ′′, b ′′, c ′′, d ′′ and parentheses is arbitrary in the formula.
  • the fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
  • the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound.
  • the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound For example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.
  • the compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (3b) rather than the compound represented by the general formula (3a) because higher surface slip properties can be obtained.
  • the mass ratio of the compound represented by the general formula (3a) and the compound represented by the general formula (3b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.
  • the fluorine-containing oil contains one or more compounds represented by the general formula (3b).
  • the mass ratio of the sum of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound in the surface treatment agent to the compound represented by formula (3b) is: It is preferably 4: 1 to 1: 4.
  • the fluorine-containing oil when the surface treatment layer is formed by a vacuum vapor deposition method, has a higher molecular weight than the average molecular weight of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound.
  • the average molecular weight may be increased. By setting such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.
  • the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group).
  • a chlorotrifluoroethylene oligomer may be sufficient.
  • the compound represented by Rf′-F and the chlorotrifluoroethylene oligomer have a high affinity with the perfluoro (poly) ether group-containing silane compound in which Rf 1 is a C 1-16 perfluoroalkyl group. preferable.
  • Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.
  • the silicone oil for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used.
  • the linear silicone oil may be so-called straight silicone oil and modified silicone oil.
  • the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil.
  • modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like.
  • Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
  • the silicone oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound (in the case of two or more types, the total of these, For example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass may be included.
  • Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.
  • the catalyst examples include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
  • acids eg, acetic acid, trifluoroacetic acid, etc.
  • bases eg, ammonia, triethylamine, diethylamine, etc.
  • transition metals eg, Ti, Ni, Sn, etc.
  • the catalyst promotes the hydrolysis and dehydration condensation of the perfluoro (poly) ether group-containing silane compound and promotes the formation of the surface treatment layer.
  • composition of the present invention may be in the form of one solution (or suspension or dispersion), or separate the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether.
  • the modified compound solution may be mixed immediately before use.
  • composition of the present invention can be made into a pellet by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form.
  • a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form.
  • the pellet can be used for, for example, vacuum deposition.
  • composition of the present invention can be suitably used as a surface treating agent because it can impart water repellency, oil repellency, antifouling property, waterproofness and high friction durability to a substrate.
  • the composition of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.
  • the article of the present invention includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the composition of the present invention.
  • This article can be manufactured, for example, as follows.
  • Substrates that can be used in the present invention include, for example, glass, sapphire glass, resin (natural or synthetic resin, such as a general plastic material, and may be a plate, film, or other form), metal ( It may be a single metal such as aluminum, copper, iron or a composite of an alloy, etc.), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be composed of any suitable material, such as a building member.
  • resin naturally or synthetic resin, such as a general plastic material, and may be a plate, film, or other form
  • metal It may be a single metal such as aluminum, copper, iron or a composite of an alloy, etc.), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be composed of any suitable material, such as a building member.
  • soda lime glass alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemical bond Particularly preferred is borosilicate glass.
  • acrylic resin and polycarbonate are preferable.
  • the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic.
  • some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate.
  • the antireflection layer either a single-layer antireflection layer or a multilayer antireflection layer may be used.
  • inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO.
  • the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be.
  • ITO indium tin oxide
  • the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
  • the shape of the substrate is not particularly limited.
  • the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
  • a base material at least a surface portion thereof may be made of a material originally having a hydroxyl group.
  • materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors.
  • it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation.
  • the plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like).
  • an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method) or chemical adsorption method. There is a method of forming in a form and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.
  • the substrate may be made of a material containing at least a surface portion of a silicone compound having one or more other reactive groups, for example, Si—H groups, or an alkoxysilane.
  • a film of the composition of the present invention is formed on the surface of the base material, and the film is post-treated as necessary, thereby forming a surface treatment layer from the composition of the present invention.
  • the film formation of the composition of the present invention can be carried out by applying the composition of the present invention to the surface of the substrate so as to cover the surface.
  • the coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
  • wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
  • Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods.
  • Specific examples of the vapor deposition method include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an ion beam, and similar methods.
  • Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
  • the composition of the present invention may be diluted with a solvent and then applied to the substrate surface.
  • a solvent preferably used: C 5-12 perfluoroaliphatic hydrocarbons such as perfluorohexane, perfluoromethylcyclohexane and perfluorohexane.
  • Fluoro-1,3-dimethylcyclohexane polyfluoroaromatic hydrocarbons (eg, bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg, C 6 F 13 CH 2 CH 3 (eg, Asahi Glass Corporation) ASAHIKLIN (registered trademark) AC-6000), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydro Fluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365mf )); Hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3) ( e.g., Sumitomo
  • 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene for example, Bertrell (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemicals
  • These solvents Can be used alone or in combination as a mixture of two or more thereof, for example, for adjusting the solubility of the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether-modified compound. In addition, it can be mixed with another solvent.
  • the composition of the present invention may be subjected to the dry coating method as it is, or may be diluted with the above-described solvent and then subjected to the dry coating method.
  • Film formation is preferably carried out so that the composition of the present invention is present together with a catalyst for hydrolysis and dehydration condensation in the film.
  • a catalyst for hydrolysis and dehydration condensation in the film.
  • the catalyst may be added to the diluted solution of the composition of the present invention immediately before application to the substrate surface.
  • the catalyst-added composition of the present invention is directly vapor-deposited (usually vacuum deposition), or a metal porous body such as iron or copper is impregnated with the catalyst-added composition of the present invention. Vapor deposition (usually vacuum deposition) may be performed using the pelletized material.
  • any suitable acid or base can be used for the catalyst.
  • the acid catalyst for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used.
  • a base catalyst ammonia, organic amines, etc. can be used, for example.
  • the membrane is post-treated as necessary.
  • this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
  • the method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
  • the supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower.
  • the pressure at this time is not specifically limited, it can be simply a normal pressure.
  • the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C.
  • the drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange
  • the above water supply and drying heating may be continuously performed by using superheated steam.
  • Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the composition of the present invention to the substrate surface, it may be allowed to stand still.
  • the surface treatment layer derived from the film of the composition of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured.
  • the surface treatment layer obtained by this has high friction durability.
  • this surface treatment layer has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), surface, etc., depending on the composition of the composition used. It can have slipperiness (or lubricity, for example, the ability to wipe off dirt such as fingerprints, and excellent touch to fingers), and can be suitably used as a functional thin film.
  • the present invention further relates to an optical material having the cured product as an outermost layer.
  • optical material in addition to optical materials relating to displays and the like exemplified below, a wide variety of optical materials are preferably mentioned: for example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Organic EL display, inorganic thin-film EL dot matrix display, rear projection display, fluorescent display tube (VFD), field emission display (FED), or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
  • CTR cathode ray tube
  • LCD liquid crystal display
  • Organic EL display organic EL display
  • inorganic thin-film EL dot matrix display rear projection display
  • fluorescent display tube (VFD), field emission display (FED) or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
  • the article having the surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member.
  • optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals.
  • the article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.
  • the thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. From the point of view, it is preferable.
  • composition of the present invention As mentioned above, the articles obtained using the composition of the present invention have been described in detail. In addition, the use of the composition of this invention, the usage method thru
  • composition of the present invention will be described in more detail through the following examples, but the present invention is not limited to these examples.
  • the chemical formulas shown below all indicate average compositions, and the order of presence of the repeating units (CF 2 CF 2 CF 2 O) constituting the perfluoropolyether is arbitrary.
  • Synthesis example 1 Synthesis of perfluoropolyether-modified methyl ester compound A reactor was charged with 240 g of methanol and 19.6 g of triethylamine, and average composition CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) at 5 ° C. in a nitrogen stream. 500 g of a perfluoropolyether-modified acid fluoro compound represented by 32 CF 2 CF 2 COF was dropped, and then the mixture was heated to room temperature and stirred. Subsequently, after adding 300 g of perfluorohexane and stirring, it was transferred to a separatory funnel and allowed to stand, and then the perfluorohexane layer was collected.
  • perfluoropolyether-modified methyl ester (A) having a methyl ester group at the terminal.
  • Synthesis example 2 Synthesis of perfluoropolyether-modified carboxylic acid compound 100 g of pure water and 20.4 g of triethylamine were charged into a reactor, and an average composition of CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O at 5 ° C. under a nitrogen stream. ) 500 g of a perfluoropolyether-modified acid fluoro compound represented by 32 CF 2 CF 2 COF was dropped, and then the mixture was heated to room temperature and stirred. Subsequently, 400 g of perfluorohexane was added and stirred, then transferred to a separatory funnel and allowed to stand, and the perfluorohexane layer was collected.
  • Synthesis example 3 Synthesis of perfluoropolyether-modified phosphate ester compound A reactor was charged with 200 g of 1,3-bis (trifluoromethyl) benzene and 54.5 g of phosphoryl chloride, and an average composition CF 3 CF 2 at 5 ° C. in a nitrogen stream. 200 g of perfluoropolyether-modified alcohol compound represented by CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OH was dropped, and then the mixture was heated to room temperature and stirred. Subsequently, after adding 400 g of perfluorohexane and stirring, 100 g of pure water was added dropwise and stirred.
  • perfluorohexane layer was collected after being transferred to a separatory funnel and allowed to stand. Subsequently, a washing operation with a 3N hydrochloric acid aqueous solution was performed. Next, 10 g of anhydrous magnesium sulfate was added to the perfluorohexane layer and stirred, and then the insoluble material was filtered off. Subsequently, volatile matter was distilled off under reduced pressure to obtain 202 g of the following perfluoropolyether-modified phosphate compound (C) having a phosphate group at the terminal.
  • Perfluoropolyether group-containing phosphate ester compound (C): CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OP ( O) (OH) 2
  • Example 1 The perfluoropolyether-modified methyl ester compound (A) obtained in Synthesis Example 1 and the perfluoropolyether-modified silane compound (X) shown below are mixed at a molar ratio of 2:98, and Novec 7200 (manufactured by 3M) The surface treating agent 1 was prepared so that it might melt
  • Perfluoropolyether modified silane compound (X) CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3
  • the surface treating agent 1 prepared above was vacuum-deposited on chemically strengthened glass (Corning, “Gorilla” glass, thickness 0.7 mm).
  • the processing conditions for vacuum deposition were set at a pressure of 3.0 ⁇ 10 ⁇ 3 Pa.
  • silicon dioxide was deposited on the surface of this chemically strengthened glass by an electron beam deposition method to a thickness of 7 nm to form a silicon dioxide film.
  • 2 mg of a surface treatment agent was vapor deposited per chemically strengthened glass (55 mm ⁇ 100 mm).
  • the chemically strengthened glass with a deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%. Thereby, a vapor deposition film hardened and a surface treatment layer was formed.
  • Example 2 Perfluoropolyether-modified compounds (A) to (C) and perfluoropolyether-modified silane compounds (X) to (Z) were mixed in the following table in a molar ratio of 2:98 to prepare a surface treatment agent.
  • a surface treatment agent was prepared in the same manner as in Example 1 except that a surface treatment layer was formed.
  • Comparative Examples 1 to 3 A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the above perfluoropolyether-modified silane compounds (X) to (Z) were used alone.
  • Comparative Example 4 A surface treatment agent was prepared in the same manner as in Example 1 except that acetic acid and the above perfluoropolyether-modified silane compound (X) were mixed at a molar ratio of 2:98 to prepare a surface treatment agent. A layer was formed.
  • the friction durability of the surface treatment layers formed on the substrate surface in Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated by an eraser friction durability test. Specifically, a sample article on which a surface treatment layer is formed is placed horizontally, and an eraser (Kokuyo Co., Ltd., KESHI-70, plane size: 1 cm ⁇ 1.6 cm) is brought into contact with the surface of the surface treatment layer. A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. The static contact angle (degree) of water was measured every 500 reciprocations. The evaluation was stopped when the measured value of the contact angle was less than 100 degrees. Finally, Table 3 shows the number of reciprocations when the contact angle exceeds 100 degrees.
  • Examples 1 to 9 in which the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether-modified compound were used in combination were compared using the perfluoro (poly) ether group-containing silane compound alone. It was confirmed to have higher eraser resistance than Examples 1 to 3.
  • the present invention is not limited by any theory, but the perfluoropolyether-modified compounds (A) to (C) act as an acidic catalyst when forming the surface treatment layer, and the perfluoro (poly) ether group-containing silane compound ( It is considered that the reactivity between X) to (Z) and the substrate surface was improved, and as a result, excellent eraser durability was obtained.
  • Example 4 using the perfluoropolyether-modified carboxylic acid compound (B) has higher eraser resistance than Comparative Example 4 using acetic acid that can simply function as a catalyst. Although this invention is not restrained by any theory, it is thought that this can contribute to the function of the surface treatment layer itself because the acid has a perfluoropolyether group.
  • the present invention can be suitably used for forming a surface treatment layer on the surface of a variety of substrates, particularly optical members that require transparency.

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Abstract

The present invention provides a composition containing: at least one type of perfluoro(poly)ether group-containing silane compound represented by any of general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) (In the formulas, each symbol has the same meaning as stated in the description); and at least one type of compound represented by formula (E1) (In the formula, each symbol has the same meaning as stated in the description).

Description

パーフルオロ（ポリ）エーテル基含有シラン化合物を含む組成物Composition comprising a perfluoro (poly) ether group-containing silane compound
　本発明は、パーフルオロ（ポリ）エーテル基含有シラン化合物を含む組成物、具体的にはパーフルオロ（ポリ）エーテル基含有シラン化合物およびパーフルオロ（ポリ）エーテル基含有酸または酸誘導体を含む組成物に関する。 The present invention relates to a composition comprising a perfluoro (poly) ether group-containing silane compound, specifically a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative. About.
　ある種の含フッ素シラン化合物は、基材の表面処理に用いると、優れた撥水性、撥油性、防汚性などを提供し得ることが知られている。含フッ素シラン化合物を含む表面処理剤から得られる層（以下、「表面処理層」とも言う）は、いわゆる機能性薄膜として、例えばガラス、プラスチック、繊維、建築資材など種々多様な基材に施されている。 It is known that certain fluorine-containing silane compounds can provide excellent water repellency, oil repellency, antifouling properties and the like when used for surface treatment of a substrate. A layer obtained from a surface treatment agent containing a fluorine-containing silane compound (hereinafter also referred to as “surface treatment layer”) is applied as a so-called functional thin film to various substrates such as glass, plastic, fiber, and building materials. ing.
　そのような含フッ素シラン化合物として、パーフルオロポリエーテル基を分子主鎖に有し、Ｓｉ原子に結合した加水分解可能な基を分子末端または末端部に有するパーフルオロポリエーテル基含有シラン化合物が知られている。例えば、特許文献１および２には、Ｓｉ原子に結合した加水分解可能な基を分子末端または末端部に有するパーフルオロポリエーテル基含有シラン化合物が記載されている。 As such a fluorine-containing silane compound, a perfluoropolyether group-containing silane compound having a perfluoropolyether group in the molecular main chain and a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part is known. It has been. For example, Patent Documents 1 and 2 describe a perfluoropolyether group-containing silane compound having a hydrolyzable group bonded to a Si atom at the molecular terminal or terminal part.
国際公開第９７／０７１５５号International Publication No. 97/07155 特表２００８－５３４６９６号公報Special table 2008-534696
　パーフルオロポリエーテル基含有シラン化合物を含む表面処理剤から得られる層は、撥水性、撥油性、防汚性などの機能を薄膜でも発揮し得ることから、光透過性および透明性が求められるメガネやタッチパネルなどの光学部材に好適に利用されている。とりわけ、これら用途においては、繰り返し摩擦を受けてもかかる機能を維持し得るように摩擦耐久性が求められる。 A layer obtained from a surface treatment agent containing a perfluoropolyether group-containing silane compound can exhibit functions such as water repellency, oil repellency, and antifouling properties even in a thin film, and thus glasses that require light transmission and transparency are required. It is suitably used for optical members such as touch panels. In particular, in these applications, friction durability is required so that such a function can be maintained even after repeated friction.
　本発明は、撥水性、撥油性、防汚性、防水性を有し、かつ、高い摩擦耐久性を有する層を形成することのできるパーフルオロ（ポリ）エーテル基含有シラン化合物を含んで成る組成物を提供することを目的とする。 The present invention relates to a composition comprising a perfluoro (poly) ether group-containing silane compound capable of forming a layer having water repellency, oil repellency, antifouling property, waterproof property and high friction durability. The purpose is to provide goods.
　本発明者らは、鋭意検討した結果、パーフルオロ（ポリ）エーテル基含有シラン化合物およびパーフルオロ（ポリ）エーテル基含有酸または酸誘導体を含んで成る組成物を用いることにより、高い摩擦耐久性を有する表面処理層を形成できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that high friction durability can be obtained by using a composition comprising a perfluoro (poly) ether group-containing silane compound and a perfluoro (poly) ether group-containing acid or acid derivative. The present inventors have found that a surface treatment layer can be formed and have completed the present invention.
　即ち、本発明の第１の要旨によれば、下記一般式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）：
Figure JPOXMLDOC01-appb-C000007
 ［式中：
　ＰＦＰＥ１は、各出現においてそれぞれ独立して、式：
　　　－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ２は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎ１は、（－ＳｉＲ１ ｎ１Ｒ２ ３－ｎ１）単位毎に独立して、０～３の整数であり；
　ただし、式（Ａ１）、（Ａ２）、（Ｂ１）および（Ｂ２）において、少なくとも１つのｎ１が、１～３の整数であり；
　Ｘ１は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
　αは、それぞれ独立して、１～９の整数であり；
　α’は、それぞれ独立して、１～９の整数であり；
　Ｘ５は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　βは、それぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｘ７は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　γは、それぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ７１ ｐ１Ｒ７２ ｑ１Ｒ７３ ｒ１を表し；
　Ｚ１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
　Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
　Ｒａ’は、Ｒａと同意義であり；
　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐ１は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑ１は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒ１は、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、式（Ｃ１）および（Ｃ２）において、少なくとも１つのｑ１が１～３の整数であり；
　Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｋ１は、各出現においてそれぞれ独立して、１～３の整数であり；
　ｌ１は、各出現においてそれぞれ独立して、０～２の整数であり；
　ｍ１は、各出現においてそれぞれ独立して、０～２の整数であり；
　Ｘ９は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　δは、それぞれ独立して、１～９の整数であり；
　δ’は、それぞれ独立して、１～９の整数であり；
　Ｒｄは、各出現においてそれぞれ独立して、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表し；
　Ｚ２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
　Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表し；
　Ｒｄ’は、Ｒｄと同意義であり；
　Ｒｄ中、Ｚ２基を介して直鎖状に連結されるＣは最大で５個であり；
　Ｒ８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
　Ｒ８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、１～３の整数を表し；
　ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｎ２は１～３の整数であり；
　Ｒ８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｒ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
　Ｒｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ｍ２は、各出現においてそれぞれ独立して、０～３の整数であり；
　ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌ２は２または３である。］
のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物、および
　下記式（Ｅ１）：
Figure JPOXMLDOC01-appb-C000008
 ［式中：
　ＰＦＰＥ２は、各出現においてそれぞれ独立して、式：
　　　－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
（式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆ２は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｚ２は、単結合または２価の有機基を表し；
　ｘは１または２であり；
　ｘが１である場合、Ａは、－ＣＯＯＲ３、－ＰＯ（ＯＲ３）２、－ＳＯ２（ＯＲ３）、または－ＳＯ（ＯＲ３）であり；
　ｘが２である場合、Ａは、－ＰＯ（ＯＲ３）－であり；
　Ｒ３は、水素原子または炭化水素基である。］
で表される少なくとも１種の化合物
を含む組成物が提供される。 That is, according to the first aspect of the present invention, the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
Figure JPOXMLDOC01-appb-C000007
 [Where:
PFPE 1 has the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of existence of each repeating unit with a, b, c, d, e or f and parenthesized is arbitrary in the formula.)
A group represented by:
Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R 1 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
R 12 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n1 is an integer of 0 to 3, independently for each (—SiR 1 n1 R 2 3-n1 ) unit;
Provided that in formulas (A1), (A2), (B1) and (B2), at least one n1 is an integer of 1 to 3;
Each X 1 independently represents a single bond or a divalent to 10-valent organic group;
X 2 represents each independently a single bond or a divalent organic group at each occurrence;
t is independently an integer from 1 to 10 at each occurrence;
each α is independently an integer from 1 to 9;
α ′ is each independently an integer of 1 to 9;
Each X 5 independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
X 7 each independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer from 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R a independently represents at each occurrence —Z 1 —SiR 71 p1 R 72 q1 R 73 r1 ;
Z 1 represents, independently at each occurrence, an oxygen atom or a divalent organic group;
R 71 independently represents R a ′ at each occurrence;
R a ′ is synonymous with R a ;
In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5;
R 72 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R 73 independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p1 is independently an integer from 0 to 3 at each occurrence;
q1 is independently an integer from 0 to 3 at each occurrence;
r1 is independently an integer from 0 to 3 at each occurrence;
Provided that in formulas (C1) and (C2), at least one q1 is an integer of 1 to 3;
R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
R c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k1 is independently an integer of 1 to 3 at each occurrence;
l1 is independently an integer from 0 to 2 at each occurrence;
m1 is independently an integer from 0 to 2 at each occurrence;
X 9 each independently represents a single bond or a divalent to 10-valent organic group;
each δ is independently an integer from 1 to 9;
each δ ′ is independently an integer from 1 to 9;
R d independently represents at each occurrence —Z 2 —CR 81 p2 R 82 q2 R 83 r2 ;
Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence;
R 81 independently represents R d ′ at each occurrence;
R d ′ is synonymous with R d ;
In R d , the maximum number of C linked in a straight chain via the Z 2 group is 5;
R 82 independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
Y represents a divalent organic group independently at each occurrence;
R 85 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R 86 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n2 represents an integer of 1 to 3 independently for each (-Y-SiR 85 n2 R 86 3-n2 ) unit;
Provided that in formulas (D1) and (D2), at least one n2 is an integer of 1 to 3;
R 83 each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
p2 is independently an integer from 0 to 3 at each occurrence;
q2 is independently an integer from 0 to 3 at each occurrence;
r2 is independently an integer from 0 to 3 at each occurrence;
R e independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
R f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
k2 is independently an integer from 0 to 3 at each occurrence;
l2 is independently an integer from 0 to 3 at each occurrence;
m2 is an integer from 0 to 3 independently at each occurrence;
However, in the formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3. ]
At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formula (E1):
Figure JPOXMLDOC01-appb-C000008
 [Where:
PFPE 2 has the formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
(Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of existence of each repeating unit with a, b, c, d, e or f and parenthesized is arbitrary in the formula.)
A group represented by:
Rf 2 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
Z 2 represents a single bond or a divalent organic group;
x is 1 or 2;
when x is 1, A is —COOR 3 , —PO (OR 3 ) 2 , —SO 2 (OR 3 ), or —SO (OR 3 );
when x is 2, A is —PO (OR 3 ) —;
R 3 is a hydrogen atom or a hydrocarbon group. ]
A composition comprising at least one compound represented by is provided.
　本発明の第２の要旨によれば、基材と、該基材の表面に、上記本発明の組成物より形成された層とを含む物品が提供される。 According to the second aspect of the present invention, there is provided an article comprising a substrate and a layer formed from the composition of the present invention on the surface of the substrate.
　本発明の第３の要旨によれば、下記式（Ｅ１）：
Figure JPOXMLDOC01-appb-C000009
 ［式中：
　Ｒｆ２は、それぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　ＰＦＰＥ２は、それぞれ独立して、－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－を表し、ここに、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり；
　Ｚ２は、単結合または２価の有機基を表し；
　ｘは１または２であり；
　ｘが１である場合、Ａは、－ＣＯＯＲ３、－ＰＯ（ＯＲ３）２、－ＳＯ２（ＯＲ３）、または－ＳＯ（ＯＲ３）であり；
　ｘが２である場合、Ａは、－ＰＯ（ＯＲ３）－であり；
　Ｒ３は、水素原子または炭化水素基である。］
で表される少なくとも１種の化合物を含む、パーフルオロ（ポリ）エーテル基含有シラン化合物の縮合促進剤が提供される。 According to the third aspect of the present invention, the following formula (E1):
Figure JPOXMLDOC01-appb-C000009
 [Where:
Each Rf 2 independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
Each of PFPE 2 is independently-(OC 6 F 12 ) a- (OC 5 F 10 ) b- (OC 4 F 8 ) c- (OC 3 F 6 ) d- (OC 2 F 4 ) e- (OCF 2) f - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f Is at least 1, and the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula;
Z 2 represents a single bond or a divalent organic group;
x is 1 or 2;
when x is 1, A is —COOR 3 , —PO (OR 3 ) 2 , —SO 2 (OR 3 ), or —SO (OR 3 );
when x is 2, A is —PO (OR 3 ) —;
R 3 is a hydrogen atom or a hydrocarbon group. ]
A perfluoro (poly) ether group-containing silane compound condensation accelerator comprising at least one compound represented by the formula:
　本発明のパーフルオロ（ポリ）エーテル基含有シラン化合物と、パーフルオロ（ポリ）エーテル基含有酸または酸誘導体とを含む組成物を用いることにより、高い摩擦耐久性を有する表面処理層を形成することができる。 A surface treatment layer having high friction durability is formed by using a composition containing the perfluoro (poly) ether group-containing silane compound of the present invention and a perfluoro (poly) ether group-containing acid or acid derivative. Can do.
　以下、本発明の組成物について説明する。 Hereinafter, the composition of the present invention will be described.
　本明細書において用いられる場合、「炭化水素基」とは、炭素および水素を含む基であって、炭化水素から１個の水素原子を脱離させた基を意味する。かかる炭化水素基としては、特に限定されるものではないが、１つまたはそれ以上の置換基により置換されていてもよい、炭素数１～２０の炭化水素基、例えば、脂肪族炭化水素基、芳香族炭化水素基等が挙げられる。上記「脂肪族炭化水素基」は、直鎖状、分枝鎖状または環状のいずれであってもよく、飽和または不飽和のいずれであってもよい。また、炭化水素基は、１つまたはそれ以上の環構造を含んでいてもよい。尚、かかる炭化水素基は、その末端または分子鎖中に、１つまたはそれ以上のＮ、Ｏ、Ｓ、Ｓｉ、アミド、スルホニル、シロキサン、カルボニル、カルボニルオキシ等を有していてもよい。 As used herein, “hydrocarbon group” means a group containing carbon and hydrogen, and a group in which one hydrogen atom has been eliminated from a hydrocarbon. Such hydrocarbon group is not particularly limited, but may be a hydrocarbon group having 1 to 20 carbon atoms which may be substituted by one or more substituents, such as an aliphatic hydrocarbon group, An aromatic hydrocarbon group etc. are mentioned. The “aliphatic hydrocarbon group” may be linear, branched or cyclic, and may be either saturated or unsaturated. The hydrocarbon group may also contain one or more ring structures. Such a hydrocarbon group may have one or more N, O, S, Si, amide, sulfonyl, siloxane, carbonyl, carbonyloxy and the like at its terminal or molecular chain.
　本明細書において用いられる場合、「炭化水素基」の置換基としては、特に限定されないが、例えば、ハロゲン原子；１個またはそれ以上のハロゲン原子により置換されていてもよい、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、Ｃ２－６アルキニル基、Ｃ３－１０シクロアルキル基、Ｃ３－１０不飽和シクロアルキル基、５～１０員のヘテロシクリル基、５～１０員の不飽和ヘテロシクリル基、Ｃ６－１０アリール基および５～１０員のヘテロアリール基から選択される１個またはそれ以上の基が挙げられる。 As used herein, the substituent of the “hydrocarbon group” is not particularly limited, but includes, for example, a halogen atom; C 1-6 alkyl optionally substituted by one or more halogen atoms Group, C 2-6 alkenyl group, C 2-6 alkynyl group, C 3-10 cycloalkyl group, C 3-10 unsaturated cycloalkyl group, 5-10 membered heterocyclyl group, 5-10 membered unsaturated heterocyclyl And one or more groups selected from a group, a C 6-10 aryl group and a 5-10 membered heteroaryl group.
　本明細書において用いられる場合、「２～１０価の有機基」とは、炭素を含有する２～１０価の基を意味する。かかる２～１０価の有機基としては、特に限定されないが、炭化水素基からさらに１～９個の水素原子を脱離させた２～１０価の基が挙げられる。例えば、２価の有機基としては、特に限定されるものではないが、炭化水素基からさらに１個の水素原子を脱離させた２価の基が挙げられる。 As used herein, “divalent to decavalent organic group” means a divalent to decavalent group containing carbon. Such a divalent to decavalent organic group is not particularly limited, and examples thereof include divalent to decavalent groups in which 1 to 9 hydrogen atoms are further eliminated from a hydrocarbon group. For example, the divalent organic group is not particularly limited, and examples thereof include a divalent group in which one hydrogen atom is further eliminated from a hydrocarbon group.
　本発明は、下記一般式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）：
Figure JPOXMLDOC01-appb-C000010
 のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物、および
　下記式（Ｅ１）：
Figure JPOXMLDOC01-appb-C000011
 で表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有酸または酸誘導体（以下、「パーフルオロ（ポリ）エーテル変性化合物」ともいう）
を含んでなる組成物を提供する（以下、「本発明の組成物」ともいう）。 The present invention includes the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
Figure JPOXMLDOC01-appb-C000010
 At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formula (E1):
Figure JPOXMLDOC01-appb-C000011
 At least one perfluoro (poly) ether group-containing acid or acid derivative (hereinafter also referred to as “perfluoro (poly) ether-modified compound”)
(Hereinafter also referred to as “the composition of the present invention”).
　以下、上記式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）で表されるパーフルオロ（ポリ）エーテル基含有シラン化合物について説明する。 Hereinafter, perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) explain.
　式（Ａ１）および（Ａ２）：
Figure JPOXMLDOC01-appb-C000012
 Formulas (A1) and (A2):
Figure JPOXMLDOC01-appb-C000012
　上記式中、ＰＦＰＥ１は、それぞれ独立して、
－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基である。式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上、例えば１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In the above formula, each PFPE 1 is independently
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
It is group represented by these. In the formula, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less. Further, the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
　これら繰り返し単位は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。例えば、－（ＯＣ６Ｆ１２）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ５Ｆ１０）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。また、－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 These repeating units may be linear or branched, but are preferably linear. For example,-(OC 6 F 12 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — , — (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred. -(OC 5 F 10 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 )) — and the like are preferable, but — ( OCF 2 CF 2 CF 2 CF 2 CF 2 ) —. -(OC 4 F 8 )-is-(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 )- ,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF ( CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably-(OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —. In addition, — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
　一の態様において、上記ＰＦＰＥ１は、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。好ましくは、ＰＦＰＥ１は、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）または－（ＯＣＦ（ＣＦ３）ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。より好ましくは、ＰＦＰＥ１は、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。 In one embodiment, the PFPE 1 is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there. Preferably, PFPE 1 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). More preferably, PFPE 1 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
　別の態様において、ＰＦＰＥ１は、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）である。、好ましくは、ＰＦＰＥ１は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ｃ－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（ＯＣＦ２ＣＦ２）ｅ－（ＯＣＦ２）ｆ－である。一の態様において、ＰＦＰＥ１は、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In another embodiment, PFPE 1 is, - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - ( wherein, c and d, respectively Each independently represents an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts c, d, The order of presence of each repeating unit in parentheses attached with e or f is arbitrary in the formula). Preferably, PFPE 1 is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —. In one embodiment, PFPE 1 is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more Preferably, it is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit with the subscript e or f and enclosed in parentheses is arbitrary in the formula).
　さらに別の態様において、ＰＦＰＥ１は、－（Ｒ６－Ｒ７）ｑ－で表される基である。式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｑは、２～１００の整数、好ましくは２～５０の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、ＰＦＰＥ１は、好ましくは、－（ＯＣ２Ｆ４－ＯＣ３Ｆ６）ｑ－または－（ＯＣ２Ｆ４－ＯＣ４Ｆ８）ｑ－である。 In still another embodiment, PFPE 1 is a group represented by — (R 6 —R 7 ) q —. In the formula, R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . In which R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups. Preferably, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups is there. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, —OC 2 F 4 OC 3 F 6 —, —OC 2 F 4 OC 4 F 8 - , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 —, —OC 3 F 6 OC 3 F 6 OC 2 F 4 —, —OC 4 F 8 OC 2 F 4 OC 2 F 4 — and the like can be mentioned. Q is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear. . In this embodiment, PFPE 1 is preferably — (OC 2 F 4 —OC 3 F 6 ) q — or — (OC 2 F 4 —OC 4 F 8 ) q —.
　上記式中、Ｒｆ１は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。 In the above formula, Rf 1 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
　上記１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基における「炭素数１～１６のアルキル基」は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のアルキル基であり、より好ましくは直鎖の炭素数１～３のアルキル基である。 The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
　上記Ｒｆ１は、好ましくは、１個またはそれ以上のフッ素原子により置換されている炭素数１～１６のアルキル基であり、より好ましくはＣＦ２Ｈ－Ｃ１－１５フルオロアルキレン基であり、さらに好ましくは炭素数１～１６のパーフルオロアルキル基である。 Rf 1 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group, A perfluoroalkyl group having 1 to 16 carbon atoms is preferred.
　該炭素数１～１６のパーフルオロアルキル基は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のパーフルオロアルキル基であり、より好ましくは直鎖の炭素数１～３のパーフルオロアルキル基、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、または－ＣＦ２ＣＦ２ＣＦ３である。 The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
　上記式中、Ｒ１は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the above formula, R 1 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
　上記「加水分解可能な基」とは、本明細書において用いられる場合、加水分解反応により、化合物の主骨格から脱離し得る基を意味する。加水分解可能な基の例としては、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝ＣＲ２、－ＮＲ２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）などが挙げられ、好ましくは－ＯＲ（即ち、アルコキシ基）である。Ｒの例には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。 The “hydrolyzable group” as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include —OR, —OCOR, —O—N═CR 2 , —NR 2 , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, and —OR (that is, an alkoxy group) is preferable. Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
　上記式中、Ｒ２は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基、好ましくは炭素数１～４のアルキル基を表す。 In the above formula, each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
　上記式中、Ｒ１１は、各出現において、それぞれ独立して、水素原子またはハロゲン原子を表す。ハロゲン原子は、好ましくはヨウ素原子、塩素原子またはフッ素原子であり、より好ましくはフッ素原子である。 In the above formulas, R 11 independently represents a hydrogen atom or a halogen atom at each occurrence. The halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
　上記式中、Ｒ１２は、各出現において、それぞれ独立して、水素原子または低級アルキル基を表す。低級アルキル基は、好ましくは炭素数１～２０のアルキル基であり、より好ましくは炭素数１～６のアルキル基であり、例えばメチル基、エチル基、プロピル基等が挙げられる。 In the above formula, R 12 each independently represents a hydrogen atom or a lower alkyl group. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
　上記式中、ｎ１は、（－ＳｉＲ１ ｎ１Ｒ２ ３－ｎ１）単位毎に独立して、０～３の整数であり、好ましくは１～３であり、より好ましくは３である。ただし、式中、すべてのｎ１が同時に０になることはない。換言すれば、式中、少なくとも１つはＲ１が存在する。 In the above formula, n1 is independently an integer of 0 to 3, preferably 1 to 3, more preferably 3, for each (-SiR 1 n1 R 2 3-n1 ) unit. However, in the formula, all n1 are not 0 at the same time. In other words, at least one R 1 is present in the formula.
　上記式中、Ｘ１は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ１は、式（Ａ１）および（Ａ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ１－ＰＦＰＥ１部または－ＰＦＰＥ１－部）と、基材との結合能を提供するシラン部（即ち、αを付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘ１は、式（Ａ１）および（Ａ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formula, each X 1 independently represents a single bond or a divalent to 10-valent organic group. X 1 is a perfluoropolyether moiety (ie, Rf 1 -PFPE 1 part or -PFPE 1 which mainly provides water repellency, surface slipperiness, etc.) in the compounds represented by formulas (A1) and (A2). -Part) and a silane part (ie, a group enclosed in parentheses with α) that provides the binding ability to the substrate. Therefore, X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.
　上記式中、αは１～９の整数であり、α’は１～９の整数である。これらαおよびα’は、Ｘ１の価数に応じて変化し得る。式（Ａ１）においては、αおよびα’の和は、Ｘ１の価数と同じである。例えば、Ｘ１が１０価の有機基である場合、αおよびα’の和は１０であり、例えばαが９かつα’が１、αが５かつα’が５、またはαが１かつα’が９となり得る。また、Ｘ１が２価の有機基である場合、αおよびα’は１である。式（Ａ２）においては、αはＸ１の価数から１を引いた値である。 In the above formula, α is an integer of 1 to 9, and α ′ is an integer of 1 to 9. These α and α ′ can vary depending on the valence of X 1 . In the formula (A1), the sum of α and α ′ is the same as the valence of X 1 . For example, when X 1 is a 10-valent organic group, the sum of α and α ′ is 10, for example, α is 9 and α ′ is 1, α is 5 and α ′ is 5, or α is 1 and α 'Can be nine. Further, when X 1 is a divalent organic group, α and α ′ are 1. In formula (A2), alpha is a value obtained by subtracting 1 from the valence of X 1.
　上記Ｘ１は、好ましくは２～７価であり、より好ましくは２～４価であり、さらに好ましくは２価の有機基である。 X 1 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
　一の態様において、Ｘ１は２～４価の有機基であり、αは１～３であり、α’は１である。 In one embodiment, X 1 is a divalent to tetravalent organic group, α is 1 to 3, and α ′ is 1.
　別の態様において、Ｘ１は２価の有機基であり、αは１であり、α’は１である。この場合、式（Ａ１）および（Ａ２）は、下記式（Ａ１’）および（Ａ２’）で表される。
Figure JPOXMLDOC01-appb-C000013
 In another embodiment, X 1 is a divalent organic group, α is 1 and α ′ is 1. In this case, the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
Figure JPOXMLDOC01-appb-C000013
　上記Ｘ１の例としては、特に限定するものではないが、例えば、下記式：
　　　－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－
［式中：
　Ｒ３１は、それぞれ独立して、単結合、－（ＣＨ２）ｓ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｓ’－であり、
　ｓ’は、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数、さらにより好ましくは１または２であり、
　Ｘａは、－（Ｘｂ）ｌ’－を表し、
　Ｘｂは、各出現においてそれぞれ独立して、－Ｏ－、－Ｓ－、ｏ－、ｍ－もしくはｐ－フェニレン基、－Ｃ（Ｏ）Ｏ－、－Ｓｉ（Ｒ３３）２－、－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、－ＣＯＮＲ３４－、－Ｏ－ＣＯＮＲ３４－、－ＮＲ３４－および－（ＣＨ２）ｎ’－からなる群から選択される基を表し、
　Ｒ３３は、各出現においてそれぞれ独立して、フェニル基、Ｃ１－６アルキル基またはＣ１－６アルコキシ基を表し、好ましくはフェニル基またはＣ１－６アルキル基であり、より好ましくはメチル基であり、
　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基（好ましくはメチル基）を表し、
　ｍ’は、各出現において、それぞれ独立して、１～１００の整数、好ましくは１～２０の整数であり、
　ｎ’は、各出現において、それぞれ独立して、１～２０の整数、好ましくは１～６の整数、より好ましくは１～３の整数であり、
　ｌ’は、１～１０の整数、好ましくは１～５の整数、より好ましくは１～３の整数であり、
　ｐ’は、０、１または２であり、
　ｑ’は、０または１であり、
　ここに、ｐ’およびｑ’の少なくとも一方は１であり、ｐ’またはｑ’を付して括弧でくくられた各繰り返し単位の存在順序は任意である。］
で表される２価の基が挙げられる。ここに、Ｒ３１およびＸａ（典型的にはＲ３１およびＸａの水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Examples of X 1 are not particularly limited, but for example, the following formula:
-(R 31 ) p ' -(X a ) q'-
[Where:
R 31 each independently represents a single bond, — (CH 2 ) s ′ — or o-, m- or p-phenylene group, preferably — (CH 2 ) s ′ —
s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
X a represents-(X b ) l ' -
X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 —, —O—CONR 34 —, —NR 34 — and — (CH 2 ) n ′ — Represents a group,
R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, and more preferably a methyl group. And
R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
l ′ is an integer of 1 to 10, preferably an integer of 1 to 5, more preferably an integer of 1 to 3,
p ′ is 0, 1 or 2;
q ′ is 0 or 1,
Here, at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses attached with p ′ or q ′ is arbitrary. ]
The bivalent group represented by these is mentioned. Here, R 31 and X a (typically a hydrogen atom of R 31 and X a ) are one or more selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group It may be substituted with a substituent.
　好ましくは、上記Ｘ１は、－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－Ｒ３２－である。Ｒ３２は、単結合、－（ＣＨ２）ｔ’－またはｏ－、ｍ－もしくはｐ－フェニレン基を表し、好ましくは－（ＣＨ２）ｔ’－である。ｔ’は、１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。ここに、Ｒ３２（典型的にはＲ３２の水素原子）は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Preferably, X 1 is — (R 31 ) p ′ — (X a ) q ′ —R 32 —. R 32 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —. t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. Here, R 32 (typically a hydrogen atom of R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
　好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－Ｒ３１－Ｘｃ－Ｒ３２－、または
－Ｘｄ－Ｒ３２－
［式中、Ｒ３１およびＲ３２は、上記と同意義である。］
であり得る。 Preferably, X 1 is
Single bond,
A C 1-20 alkylene group,
-R 31 -X c -R 32- , or -X d -R 32-
[Wherein, R 31 and R 32 are as defined above. ]
It can be.
　より好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－
－Ｘｄ－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、ｓ’およびｔ’は、上記と同意義である。］
である。 More preferably, said X 1 is
Single bond,
A C 1-20 alkylene group,
-(CH 2 ) s' -X c- ,
-(CH 2 ) s ' -X c- (CH 2 ) t'-
-X d- , or -X d- (CH 2 ) t ' -
[Wherein, s ′ and t ′ are as defined above]. ]
It is.
　上記式中、Ｘｃは、
－Ｏ－、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ３４－、
－Ｏ－ＣＯＮＲ３４－、
－Ｓｉ（Ｒ３３）２－、
－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（Ｒ３３）２－Ｏ－Ｓｉ（Ｒ３３）２－ＣＨ２ＣＨ２－Ｓｉ（Ｒ３３）２－Ｏ－Ｓｉ（Ｒ３３）２－、
－Ｏ－（ＣＨ２）u’－Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－Ｎ（Ｒ３４）－、または
－ＣＯＮＲ３４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ３３）２－
［式中、Ｒ３３、Ｒ３４およびｍ’は、上記と同意義であり、
　ｕ’は１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］を表す。Ｘｃは、好ましくは－Ｏ－である。 In the above formula, X c is
-O-,
-S-,
-C (O) O-,
-CONR 34 -,
-O-CONR 34 -,
-Si (R 33 ) 2- ,
-(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- ,
—O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —,
—O— (CH 2 ) u ′ —Si (R 33 ) 2 —O—Si (R 33 ) 2 —CH 2 CH 2 —Si (R 33 ) 2 —O—Si (R 33 ) 2 —,
—O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —,
—CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —,
—CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 —
[Wherein, R 33 , R 34 and m ′ are as defined above;
u ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3. ]. X c is preferably —O—.
　上記式中、Ｘｄは、
－Ｓ－、
－Ｃ（Ｏ）Ｏ－、
－ＣＯＮＲ３４－、
－ＣＯＮＲ３４－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－、
－ＣＯＮＲ３４－（ＣＨ２）u’－Ｎ（Ｒ３４）－、または
－ＣＯＮＲ３４－（ｏ－、ｍ－またはｐ－フェニレン）－Ｓｉ（Ｒ３３）２－
［式中、各記号は、上記と同意義である。］
を表す。 In the above formula, X d is
-S-,
-C (O) O-,
-CONR 34 -,
—CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —,
—CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 —
[Wherein each symbol is as defined above. ]
Represents.
　より好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｘｃ－（ＣＨ２）ｔ’－、または
－Ｘｄ－（ＣＨ２）ｔ’－
［式中、各記号は、上記と同意義である。］
であり得る。 More preferably, said X 1 is
Single bond,
A C 1-20 alkylene group,
— (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ —
[Wherein each symbol is as defined above. ]
It can be.
　さらにより好ましくは、上記Ｘ１は、
単結合、
Ｃ１－２０アルキレン基、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（ＣＨ２）ｔ’－、
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）u’－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（ＣＨ２）ｔ’－、または
－（ＣＨ２）ｓ’－Ｏ－（ＣＨ２）ｔ’－Ｓｉ（Ｒ３３）２ －（ＣＨ２）u’－Ｓｉ（Ｒ３３）２－（ＣvＨ２v）－
［式中、Ｒ３３、ｍ’、ｓ’、ｔ’およびｕ’は、上記と同意義であり、ｖは１～２０の整数、好ましくは２～６の整数、より好ましくは２～３の整数である。］
である。 Even more preferably, said X 1 is
Single bond,
A C 1-20 alkylene group,
— (CH 2 ) s ′ —O— (CH 2 ) t ′ —,
- (CH 2) s' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -,
— (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s′— O— (CH 2 ) t ′ —Si (R 33 ) 2 — (CH 2 ) u ′ —Si (R 33 ) 2 — (C v H 2v ) —
Wherein R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 2 to 3. It is an integer. ]
It is.
　上記式中、－（ＣvＨ２v）－は、直鎖であっても、分枝鎖であってもよく、例えば、－ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＣＨ（ＣＨ３）ＣＨ２－であり得る。 In the above formula, — (C v H 2v ) — may be linear or branched. For example, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH It may be (CH 3 ) —, —CH (CH 3 ) CH 2 —.
　上記Ｘ１基は、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基（好ましくは、Ｃ１－３パーフルオロアルキル基）から選択される１個またはそれ以上の置換基により置換されていてもよい。 The X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). May be.
　別の態様において、Ｘ１基としては、例えば下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
 ［式中、Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基、好ましくはメチル基であり；
　Ｄは、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、および
Figure JPOXMLDOC01-appb-C000016
 （式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。）
から選択される基であり、
　Ｅは、－（ＣＨ２）ｎ－（ｎは２～６の整数）であり、
　Ｄは、分子主鎖のＰＦＰＥ１に結合し、Ｅは、ＰＦＰＥ１と反対の基に結合する。］ In another embodiment, examples of X 1 groups include the following groups:
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
 [Wherein, each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
D is
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CF 2 O (CH 2 ) 3 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), and
Figure JPOXMLDOC01-appb-C000016
 (In the formula, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.)
A group selected from
E is — (CH 2 ) n — (n is an integer of 2 to 6);
D binds to PFPE 1 in the molecular backbone, and E binds to the opposite group to PFPE 1 . ]
　上記Ｘ１の具体的な例としては、例えば：
単結合、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000017
 などが挙げられる。 Specific examples of X 1 include, for example:
Single bond,
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —
—CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—CH 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
— (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000017
 Etc.
　さらに別の態様において、Ｘ１は、式：－（Ｒ１６）ｘ－（ＣＦＲ１７）ｙ－（ＣＨ２）ｚ－で表される基である。式中、ｘ、ｙおよびｚは、それぞれ独立して、０～１０の整数であり、ｘ、ｙおよびｚの和は１以上であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In still another embodiment, X 1 is a group represented by the formula: — (R 16 ) x — (CFR 17 ) y — (CH 2 ) z —. In the formula, x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is Is optional.
　上記式中、Ｒ１６は、各出現においてそれぞれ独立して、酸素原子、フェニレン、カルバゾリレン、－ＮＲ２６－（式中、Ｒ２６は、水素原子または有機基を表す）または２価の有機基である。好ましくは、Ｒ１６は、酸素原子または２価の極性基である。 In the above formula, R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 26 — (wherein R 26 represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there. Preferably, R 16 is an oxygen atom or a divalent polar group.
　上記「２価の極性基」としては、特に限定されないが、－Ｃ（Ｏ）－、－Ｃ（＝ＮＲ２７）－、および－Ｃ（Ｏ）ＮＲ２７－（これらの式中、Ｒ２７は、水素原子または低級アルキル基を表す）が挙げられる。当該「低級アルキル基」は、例えば、炭素数１～６のアルキル基、例えばメチル、エチル、ｎ－プロピルであり、これらは、１個またはそれ以上のフッ素原子により置換されていてもよい。 The “divalent polar group” is not particularly limited, but —C (O) —, —C (═NR 27 ) —, and —C (O) NR 27 — (in these formulas, R 27 is Represents a hydrogen atom or a lower alkyl group). The “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.
　上記式中、Ｒ１７は、各出現においてそれぞれ独立して、水素原子、フッ素原子または低級フルオロアルキル基であり、好ましくはフッ素原子である。当該「低級フルオロアルキル基」は、例えば、炭素数１～６、好ましくは炭素数１～３のフルオロアルキル基、好ましくは炭素数１～３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、さらに好ましくはトリフルオロメチル基である。 In the above formula, R 17 is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence. The “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.
　この態様において、Ｘ１は、好ましくは、式：－（Ｏ）ｘ－（ＣＦ２）ｙ－（ＣＨ２）ｚ－（式中、ｘ、ｙおよびｚは、上記と同意義であり、括弧でくくられた各繰り返し単位の存在順序は式中において任意である）で表される基である。 In this embodiment, X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above The order in which each repeating unit is included is arbitrary in the formula).
　上記式：－（Ｏ）ｘ－（ＣＦ２）ｙ－（ＣＨ２）ｚ－で表される基としては、例えば、－（Ｏ）ｘ’－（ＣＨ２）ｚ”－Ｏ－［（ＣＨ２）ｚ’’’－Ｏ－］ｚ””、および－（Ｏ）ｘ’－（ＣＦ２）ｙ”－（ＣＨ２）ｚ”－Ｏ－［（ＣＨ２）ｚ’’’－Ｏ－］ｚ””（式中、ｘ’は０または１であり、ｙ”、ｚ”およびｚ’’’は、それぞれ独立して、１～１０の整数であり、ｚ””は、０または１である）で表される基が挙げられる。なお、これらの基は左端がＰＦＰＥ１側に結合する。 Examples of the group represented by the above formula: — (O) x — (CF 2 ) y — (CH 2 ) z — include, for example, — (O) x ′ — (CH 2 ) z ″ —O — [(CH 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z" -O - [(CH 2) z '''-O- Z ″ ″ (wherein x ′ is 0 or 1, y ″, z ″ and z ′ ″ are each independently an integer of 1 to 10, and z ″ ″ is 0 or 1) These groups are bonded at the left end to the PFPE 1 side.
　別の好ましい態様において、Ｘ１は、－Ｏ－ＣＦＲ１３－（ＣＦ２）ｇ－である。 In another preferred embodiment, X 1 is —O—CFR 13 — (CF 2 ) g —.
　上記Ｒ１３は、それぞれ独立して、フッ素原子または低級フルオロアルキル基を表す。低級フルオロアルキル基は、例えば炭素数１～３のフルオロアルキル基、好ましくは炭素数１～３のパーフルオロアルキル基、より好ましくはトリフルオロメチル基、ペンタフルオロエチル基、更に好ましくはトリフルオロメチル基である。 Each R 13 independently represents a fluorine atom or a lower fluoroalkyl group. The lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
　上記ｇは、それぞれ独立して、０または１である。 The above g is independently 0 or 1.
　一の具体例において、Ｒ１３はフッ素原子であり、ｅは１である。 In one embodiment, R 13 is a fluorine atom and e is 1.
　さらに別の態様において、Ｘ１は、－Ｘｃ－ＣＯ－ＮＲ１４－Ｘｄ－または－Ｘｃ－ＣＯ－Ｎ（－Ｘｄ－）２で表される基である。－Ｘｃ－ＣＯ－ＮＲ１４－Ｘｄ－が、２価の基であり、－Ｘｃ－ＣＯ－Ｎ（－Ｘｄ－）２は３価の基である。 In still another embodiment, X 1 is a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 . —X c —CO—NR 14 —X d — is a divalent group, and —X c —CO—N (—X d —) 2 is a trivalent group.
　Ｒ１４は、水素原子、低級アルキル基またはフェニル基を表す。低級アルキル基は、好ましくはＣ１－６アルキル基、より好ましくはＣ１－３のアルキル基、さらに好ましくはメチル基であり得る。 R 14 represents a hydrogen atom, a lower alkyl group or a phenyl group. The lower alkyl group may be preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a methyl group.
　上記Ｘｃは、単結合または２価の有機基を表す。 Xc represents a single bond or a divalent organic group.
　上記Ｘｃにおける２価の有機基は、好ましくは、
－（ＣＲ８ ２）ｋ１－（Ｏ）ｋ２－（ＮＲ９）ｋ３－
［式中：
　Ｒ８は、それぞれ独立して、水素原子またはフッ素原子であり；
　Ｒ９は、それぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基を表し；
　ｋ１は、１～２０の整数であり；
　ｋ２は、０～１０の整数であり；
　ｋ３は、０～１０の整数であり；
　ここに、ｋ１、ｋ２またはｋ３を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
で表される基であり得る。 The divalent organic group in Xc is preferably,
-(CR 8 2 ) k1- (O) k2- (NR 9 ) k3-
[Where:
Each R 8 is independently a hydrogen atom or a fluorine atom;
Each R 9 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
k1 is an integer from 1 to 20;
k2 is an integer from 0 to 10;
k3 is an integer from 0 to 10;
Here, k 1, k 2 or k 3 is attached in parentheses, and the order of existence of each repeating unit is arbitrary in the formula. ]
It can be group represented by these.
　上記Ｘｄは、２価の有機基を表す。 Xd represents a divalent organic group.
　上記Ｘｄにおける２価の有機基は、好ましくは、
－（ＣＲ２０ ２）ｋ４－（Ｏ）ｋ５－（ＮＲ２１）ｋ６－、
［式中：
　Ｒ２０は、それぞれ独立して、水素原子またはフッ素原子であり；
　Ｒ２１は、それぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基を表し；
　ｋ４は、１～２０の整数であり；
　ｋ５は、０～１０の整数であり；
　ｋ６は、０～１０の整数であり；
　ここに、ｋ４、ｋ５またはｋ６を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
で表される基であり得る。 The divalent organic group in X d is preferably
- (CR 20 2) k4 - (O) k5 - (NR 21) k6 -,
[Where:
Each R 20 is independently a hydrogen atom or a fluorine atom;
Each R 21 independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
k4 is an integer from 1 to 20;
k5 is an integer from 0 to 10;
k6 is an integer from 0 to 10;
Here, k4, k5 or k6 is added in parentheses, and the order of existence of each repeating unit is arbitrary in the formula. ]
It can be group represented by these.
　一の態様において、Ｘｃは、－（ＣＦ２）ｋ１’－または－（ＣＦ２）ｋ１’－（Ｏ）ｋ２’－
［式中：
　ｋ１’は、１～６の整数であり；
　ｋ２’は、１～３の整数であり；
　ここに、ｋ１’またはｋ２’を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
であり、
　Ｘｄは、－（ＣＨ２）ｋ４’－または－（ＣＨ２）ｋ４’－Ｏｋ５’－
［式中：
　ｋ４’は、１～６の整数であり；
　ｋ５’は、１～３の整数であり；
　ここに、ｋ４’またはｋ５’を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
である。 In one embodiment, X c is — (CF 2 ) k1 ′ — or — (CF 2 ) k1 ′ — (O) k2 ′ —.
[Where:
k1 ′ is an integer from 1 to 6;
k2 ′ is an integer from 1 to 3;
Here, k1 ′ or k2 ′ is added in parentheses, and the order of existence of each repeating unit is arbitrary in the formula. ]
And
X d represents — (CH 2 ) k4 ′ — or — (CH 2 ) k4 ′ —O k5 ′ —.
[Where:
k4 ′ is an integer from 1 to 6;
k5 ′ is an integer from 1 to 3;
Here, k4 ′ or k5 ′ is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ]
It is.
　さらに別の態様において、Ｘ１基の例として、下記の基が挙げられる：
Figure JPOXMLDOC01-appb-C000018
 ［式中、
　Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルキル基、またはＣ１－６アルコキシ基好ましくはメチル基であり；
　各Ｘ１基において、Ｔのうち任意のいくつかは、分子主鎖のＰＦＰＥ１に結合する以下の基：
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＦ２Ｏ（ＣＨ２）３－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）4－、
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、または
Figure JPOXMLDOC01-appb-C000019
 ［式中、Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基、好ましくはメチル基またはメトキシ基、より好ましくはメチル基を表す。］
であり、別のＴのいくつかは、分子主鎖のＰＦＰＥ１と反対の基（即ち、式（Ａ１）、
（Ａ２）、（Ｄ１）および（Ｄ２）においては炭素原子、また、下記する式（Ｂ１）、（Ｂ２）、（Ｃ１）および（Ｃ２）においてはＳｉ原子）に結合する－（ＣＨ２）ｎ”－（ｎ”は２～６の整数）であり、存在する場合、残りは、それぞれ独立して、メチル基、フェニル基、Ｃ１－６アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。 In yet another embodiment, examples of X 1 groups include the following groups:
Figure JPOXMLDOC01-appb-C000018
 [Where:
Each of R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
In each X 1 group, any some of T are bound to the PFPE 1 of the molecular backbone:
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CF 2 O (CH 2 ) 3 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), or
Figure JPOXMLDOC01-appb-C000019
 [Wherein, each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group. ]
And some of the other T are groups opposite to PFPE 1 of the molecular backbone (ie, formula (A1),
— (CH 2 ) n bonded to a carbon atom in (A2), (D1) and (D2), and to a Si atom in the following formulas (B1), (B2), (C1) and (C2)) “ — (N” is an integer of 2 to 6), and when present, the remainder can each independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, a radical scavenging group or an ultraviolet absorbing group. .
　ラジカル捕捉基は、光照射で生じるラジカルを捕捉できるものであれば特に限定されないが、例えばベンゾフェノン類、ベンゾトリアゾール類、安息香酸エステル類、サリチル酸フェニル類、クロトン酸類、マロン酸エステル類、オルガノアクリレート類、ヒンダードアミン類、ヒンダードフェノール類、またはトリアジン類の残基が挙げられる。 The radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation. For example, benzophenones, benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates , Hindered amines, hindered phenols, or triazine residues.
　紫外線吸収基は、紫外線を吸収できるものであれば特に限定されないが、例えばベンゾトリアゾール類、ヒドロキシベンゾフェノン類、置換および未置換安息香酸もしくはサリチル酸化合物のエステル類、アクリレートまたはアルコキシシンナメート類、オキサミド類、オキサニリド類、ベンゾキサジノン類、ベンゾキサゾール類の残基が挙げられる。 The ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays. For example, benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides, Examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
　好ましい態様において、好ましいラジカル捕捉基または紫外線吸収基としては、
Figure JPOXMLDOC01-appb-C000020
 が挙げられる。 In a preferred embodiment, preferred radical scavenging groups or ultraviolet absorbing groups include
Figure JPOXMLDOC01-appb-C000020
 Is mentioned.
　この態様において、Ｘ１は、それぞれ独立して、３～１０価の有機基であり得る。 In this embodiment, X 1 can be each independently a trivalent to 10 valent organic group.
　上記式中、ｔは、それぞれ独立して、１～１０の整数である。好ましい態様において、ｔは１～６の整数である。別の好ましい態様において、ｔは２～１０の整数であり、好ましくは２～６の整数である。 In the above formula, t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.
　上記式中、Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表す。Ｘ２は、好ましくは、炭素数１～２０のアルキレン基であり、より好ましくは、－（ＣＨ２）ｕ－（式中、ｕは、０～２の整数である）である。 In the above formula, X 2 independently represents a single bond or a divalent organic group at each occurrence. X 2 is preferably an alkylene group having 1 to 20 carbon atoms, more preferably, - (CH 2) u - ( wherein, u is an integer of 0 to 2) a.
　好ましい式（Ａ１）および（Ａ２）で示される化合物は、下記式（Ａ１’）および（Ａ２’）：
Figure JPOXMLDOC01-appb-C000021
 ［式中：
　ＰＦＰＥ１は、それぞれ独立して、式：
　　　　－（ＯＣ４Ｆ８）ａ－（ＯＣ３Ｆ６）ｂ－（ＯＣ２Ｆ４）ｃ－（ＯＣＦ２）ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり； 
　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ２は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｎ１は、１～３の整数であり、好ましくは３であり；
　Ｘ１は、－Ｏ－ＣＦＲ１３－（ＣＦ２）ｅ－であり； 
　Ｒ１３は、フッ素原子または低級フルオロアルキル基であり；
　ｅは、０または１であり；
　Ｘ２は、－（ＣＨ２）ｕ－であり；
　ｕは、０～２の整数であり（ｕが０の場合Ｘ２は単結合である）；
　ｔは、１～１０の整数である。］
で表される化合物である。 Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′):
Figure JPOXMLDOC01-appb-C000021
 [Where:
Each PFPE 1 is independently of the formula:
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R 1 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
R 12 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
n1 is an integer from 1 to 3, preferably 3;
X 1 is —O—CFR 13 — (CF 2 ) e —;
R 13 is a fluorine atom or a lower fluoroalkyl group;
e is 0 or 1;
X 2 is — (CH 2 ) u —;
u is an integer from 0 to 2 (when u is 0, X 2 is a single bond);
t is an integer of 1 to 10. ]
It is a compound represented by these.
　上記式（Ａ１）および（Ａ２）で表される化合物は、例えば、Ｒｆ１－ＰＦＰＥ１－部分に対応するパーフルオロポリエーテル誘導体を原料として、末端にヨウ素を導入した後、－ＣＨ２ＣＲ１２（Ｘ２－ＳｉＲ１ ｎ１Ｒ２ ３－ｎ１）－に対応するビニルモノマーを反応させることにより得ることができる。 The compounds represented by the above formulas (A1) and (A2) can be prepared by, for example, using perfluoropolyether derivative corresponding to Rf 1 -PFPE 1 -moiety as a raw material, introducing iodine at the terminal, and then —CH 2 CR 12 It can be obtained by reacting a vinyl monomer corresponding to (X 2 —SiR 1 n1 R 2 3-n1 ) —.
　式（Ｂ１）および（Ｂ２）：
Figure JPOXMLDOC01-appb-C000022
 Formulas (B1) and (B2):
Figure JPOXMLDOC01-appb-C000022
　上記式（Ｂ１）および（Ｂ２）中、Ｒｆ１、ＰＦＰＥ１、Ｒ１、Ｒ２およびｎ１は、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (B1) and (B2), Rf 1 , PFPE 1 , R 1 , R 2 and n1 are the same as those described for the above formulas (A1) and (A2).
　上記式中、Ｘ５は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ５は、式（Ｂ１）および（Ｂ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（Ｒｆ１－ＰＦＰＥ１部または－ＰＦＰＥ１－部）と、基材との結合能を提供するシラン部（具体的には、－ＳｉＲ１ ｎ１Ｒ２ ３－ｎ１）とを連結するリンカーと解される。従って、当該Ｘ５は、式（Ｂ１）および（Ｂ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulas, X 5 each independently represents a single bond or a divalent to 10-valent organic group. The X 5 is a perfluoropolyether part (Rf 1 -PFPE 1 part or -PFPE 1 -part) which mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (B1) and (B2). ) And a silane moiety (specifically, —SiR 1 n1 R 2 3-n1 ) that provides the binding ability to the base material. Therefore, X 5 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.
　上記式中のβは、１～９の整数であり、β’は、１～９の整数である。これらβおよびβ’は、Ｘ３の価数に応じて決定され、式（Ｂ１）において、βおよびβ’の和は、Ｘ５の価数と同じである。例えば、Ｘ５が１０価の有機基である場合、βおよびβ’の和は１０であり、例えばβが９かつβ’が１、βが５かつβ’が５、またはβが１かつβ’が９となり得る。また、Ｘ５が２価の有機基である場合、βおよびβ’は１である。式（Ｂ２）において、βはＸ５の価数の値から１を引いた値である。 In the above formula, β is an integer of 1 to 9, and β ′ is an integer of 1 to 9. These β and β ′ are determined according to the valence of X 3 , and in the formula (B1), the sum of β and β ′ is the same as the valence of X 5 . For example, when X 5 is a 10-valent organic group, the sum of β and β ′ is 10, for example, β is 9 and β ′ is 1, β is 5 and β ′ is 5, or β is 1 and β 'Can be nine. When X 5 is a divalent organic group, β and β ′ are 1. In formula (B2), beta is a value obtained by subtracting 1 from the valence of the value of X 5.
　上記Ｘ５は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 X 5 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
　一の態様において、Ｘ５は２～４価の有機基であり、βは１～３であり、β’は１である。 In one embodiment, X 5 is a divalent to tetravalent organic group, β is 1 to 3, and β ′ is 1.
　別の態様において、Ｘ５は２価の有機基であり、βは１であり、β’は１である。この場合、式（Ｂ１）および（Ｂ２）は、下記式（Ｂ１’）および（Ｂ２’）で表される。
Figure JPOXMLDOC01-appb-C000023
 In another embodiment, X 5 is a divalent organic group, β is 1 and β ′ is 1. In this case, the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
Figure JPOXMLDOC01-appb-C000023
　上記Ｘ５の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 5 are not particularly limited, and examples thereof include those similar to those described for X 1 .
　一の好ましい態様として、Ｘ５は、－Ｘｃ－ＣＯ－ＮＲ１４－Ｘｄ－または－Ｘｃ－ＣＯ－Ｎ（－Ｘｄ－）２で表される基であり得る。Ｘｃ、ＸｄおよびＲ１４は、上記Ｘ１についての記載と同位置である。 In one preferred embodiment, X 5 may be a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 . X c , X d and R 14 are in the same positions as described for X 1 above.
　好ましい具体的なＸ５は、
単結合、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000024
 などが挙げられる。 Preferred specific X 5 is
Single bond,
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —
—CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—CH 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
— (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000024
 Etc.
　好ましい式（Ｂ１）および（Ｂ２）で示される化合物は、下記式（Ｂ１’）および（Ｂ２’）：
Figure JPOXMLDOC01-appb-C000025
 ［式中：
　ＰＦＰＥ１は、それぞれ独立して、式：
　　　　－（ＯＣ４Ｆ８）ａ－（ＯＣ３Ｆ６）ｂ－（ＯＣ２Ｆ４）ｃ－（ＯＣＦ２）ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｒ１は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ２は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
　ｎ１は、１～３の整数であり、好ましくは３であり；
　Ｘ５は、－ＣＨ２Ｏ（ＣＨ２）２－、－ＣＨ２Ｏ（ＣＨ２）３－または－ＣＨ２Ｏ（ＣＨ２）６－である］
で表される化合物である。 Preferred compounds represented by formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′):
Figure JPOXMLDOC01-appb-C000025
 [Where:
Each PFPE 1 is independently of the formula:
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
R 1 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
n1 is an integer from 1 to 3, preferably 3;
X 5 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 —
It is a compound represented by these.
　上記式（Ｂ１）および（Ｂ２）で表される化合物は、公知の方法、例えば特許文献１に記載の方法またはその改良方法により製造することができる。例えば、式（Ｂ１）および（Ｂ２）で表される化合物は、下記式（Ｂ１－４）または（Ｂ２－４）：
Figure JPOXMLDOC01-appb-C000026
 ［式中：
　ＰＦＰＥ１は、それぞれ独立して、式：
　　　　－（ＯＣ４Ｆ８）ａ－（ＯＣ３Ｆ６）ｂ－（ＯＣ２Ｆ４）ｃ－（ＯＣＦ２）ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｘ５’は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　βは、それぞれ独立して、１～９の整数であり；
　β’は、それぞれ独立して、１～９の整数であり；
　Ｒ９２は、単結合または２価の有機基である。］
で表される化合物を、ＨＳｉＭ３（式中、Ｍは、それぞれ独立して、ハロゲン原子、Ｒ１またはＲ２であり、Ｒ１は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基であり、Ｒ２は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基である）と反応させて、必要に応じて、上記ハロゲン原子を、Ｒ１またはＲ２に変換して、式（Ｂ１”）または（Ｂ２”）：
Figure JPOXMLDOC01-appb-C000027
 ［式中、ＰＦＰＥ１、Ｒｆ１、Ｘ５’、β、β’およびＲ９２は、上記と同意義であり；
　ｎ１は、０～３の整数である。］
で表される化合物として得ることができる。 The compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in Patent Document 1 or an improved method thereof. For example, the compounds represented by the formulas (B1) and (B2) are represented by the following formulas (B1-4) or (B2-4):
Figure JPOXMLDOC01-appb-C000026
 [Where:
Each PFPE 1 is independently of the formula:
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
Each X 5 ′ independently represents a single bond or a divalent to 10-valent organic group;
each β is independently an integer from 1 to 9;
each β ′ is independently an integer from 1 to 9;
R 92 is a single bond or a divalent organic group. ]
HSiM 3 (wherein, M is independently a halogen atom, R 1 or R 2 , and R 1 is independently a hydroxyl group or hydrolyzable at each occurrence) R 2 is independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence, and the halogen atom is optionally substituted with R 1 or R 2. Into the formula (B1 ″) or (B2 ″):
Figure JPOXMLDOC01-appb-C000027
 [Wherein, PFPE 1 , Rf 1 , X 5 ′ , β, β ′ and R 92 are as defined above;
n1 is an integer of 0 to 3. ]
It can obtain as a compound represented by these.
　式（Ｂ１”）または（Ｂ２”）において、Ｘ５’からＲ９２－ＣＨ２ＣＨ２－までの部分が、式（Ｂ１）または（Ｂ２）におけるＸ５に対応する。 In the formula (B1 ″) or (B2 ″), the portion from X 5 ′ to R 92 —CH 2 CH 2 — corresponds to X 5 in the formula (B1) or (B2).
　式（Ｃ１）および（Ｃ２）：
Figure JPOXMLDOC01-appb-C000028
 Formulas (C1) and (C2):
Figure JPOXMLDOC01-appb-C000028
　上記式（Ｃ１）および（Ｃ２）中、Ｒｆ１およびＰＦＰＥ１は、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (C1) and (C2), Rf 1 and PFPE 1 are the same as those described for the above formulas (A1) and (A2).
　上記式中、Ｘ７は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘ７は、式（Ｃ１）および（Ｃ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（Ｒｆ１－ＰＦＰＥ１部または－ＰＦＰＥ１－部）と、基材との結合能を提供するシラン部（具体的には、－ＳｉＲａ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１基）とを連結するリンカーと解される。従って、当該Ｘ７は、式（Ｃ１）および（Ｃ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulae, X 7 each independently represents a single bond or a divalent to 10-valent organic group. The X 7 is a perfluoropolyether part (Rf 1 -PFPE 1 part or -PFPE 1 -part) which mainly provides water repellency and surface slipperiness in the compounds represented by the formulas (C1) and (C2). ) And a silane moiety (specifically, —SiR a k1 R b 11 R c m1 group) that provides the binding ability to the base material. Therefore, X 7 may be any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.
　上記式中のγは、１～９の整数であり、γ’は、１～９の整数である。これらγおよびγ’は、Ｘ７の価数に応じて決定され、式（Ｃ１）において、γおよびγ’の和は、Ｘ７の価数と同じである。例えば、Ｘ７が１０価の有機基である場合、γおよびγ’の和は１０であり、例えばγが９かつγ’が１、γが５かつγ’が５、またはγが１かつγ’が９となり得る。また、Ｘ７が２価の有機基である場合、γおよびγ’は１である。式（Ｃ１）において、γはＸ７の価数の値から１を引いた値である。 In the above formula, γ is an integer of 1 to 9, and γ ′ is an integer of 1 to 9. These γ and γ ′ are determined according to the valence of X 7 , and in the formula (C1), the sum of γ and γ ′ is the same as the valence of X 7 . For example, when X 7 is a 10-valent organic group, the sum of γ and γ ′ is 10, for example, γ is 9 and γ ′ is 1, γ is 5 and γ ′ is 5, or γ is 1 and γ. 'Can be nine. Further, when X 7 is a divalent organic group, γ and γ ′ are 1. In formula (C1), gamma is a value obtained by subtracting 1 from the valence of the values of X 7.
　上記Ｘ７は、好ましくは２～７価、より好ましくは２～４価、さらに好ましくは２価の有機基である。 X 7 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
　一の態様において、Ｘ７は２～４価の有機基であり、γは１～３であり、γ’は１である。 In one embodiment, X 7 is a divalent to tetravalent organic group, γ is 1 to 3, and γ ′ is 1.
　別の態様において、Ｘ７は２価の有機基であり、γは１であり、γ’は１である。この場合、式（Ｃ１）および（Ｃ２）は、下記式（Ｃ１’）および（Ｃ２’）で表される。
Figure JPOXMLDOC01-appb-C000029
 In another embodiment, X 7 is a divalent organic group, γ is 1 and γ ′ is 1. In this case, the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
Figure JPOXMLDOC01-appb-C000029
　上記Ｘ７の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 7 are not particularly limited, and examples thereof include those similar to those described for X 1 .
　一の好ましい態様として、Ｘ５は、－Ｘｃ－ＣＯ－ＮＲ１４－Ｘｄ－または－Ｘｃ－ＣＯ－Ｎ（－Ｘｄ－）２で表される基であり得る。ＸｃおよびＸｄは、上記Ｘ１についての記載と同位置である。 In one preferred embodiment, X 5 may be a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 . X c and X d are the same positions as described for X 1 above.
　好ましい具体的なＸ７は、
単結合、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000030
 などが挙げられる。 Preferred specific X 7 is
Single bond,
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —
—CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—CH 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
— (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000030
 Etc.
　上記式中、Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ７１ ｐ１Ｒ７２ ｑ１Ｒ７３ ｒ１を表す。 In the above formula, R a independently represents —Z 1 —SiR 71 p1 R 72 q1 R 73 r1 at each occurrence.
　式中、Ｚ１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表す。 In the formula, Z 1 represents an oxygen atom or a divalent organic group independently at each occurrence.
　上記Ｚ１は、好ましくは、２価の有機基であり、式（Ｃ１）または式（Ｃ２）における分子主鎖の末端のＳｉ原子（Ｒａが結合しているＳｉ原子）とシロキサン結合を形成するものを含まない。 Z 1 is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which R a is bonded) at the end of the molecular main chain in formula (C1) or formula (C2). Does not include what to do.
　上記Ｚ１は、好ましくは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ－Ｏ－（ＣＨ２）ｈ－（式中、ｇは、１～６の整数であり、ｈは、１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ－（式中、ｉは、０～６の整数である）であり、より好ましくはＣ１－３アルキレン基である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Z 1 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 1 to 6, and h is 1 to 6 is an integer of 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　式中、Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表す。Ｒａ’は、Ｒａと同意義である。 In the formula, R 71 represents R a ′ independently at each occurrence. R a ′ has the same meaning as R a .
　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個である。即ち、上記Ｒａにおいて、Ｒ７１が少なくとも１つ存在する場合、Ｒａ中にＺ１基を介して直鎖状に連結されるＳｉ原子が２個以上存在するが、かかるＺ基を介して直鎖状に連結されるＳｉ原子の数は最大で５個である。なお、「Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数」とは、Ｒａ中において直鎖状に連結される－Ｚ１－Ｓｉ－の繰り返し数と等しくなる。 In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5. That is, in the above R a , when at least one R 71 is present, there are two or more Si atoms linearly linked through the Z 1 group in R a. The maximum number of Si atoms connected in a straight line is five. The "number of Si atoms linearly linked via a Z group in R a" is equal to -Z 1 -Si- repetition rate of which is connected to a linear during R a .
　例えば、下記にＲａ中においてＺ１基（下記では単に「Ｚ」と示す）を介してＳｉ原子が連結された一例を示す。
Figure JPOXMLDOC01-appb-C000031
 For example, an example in which Si atoms are connected to each other through a Z 1 group (hereinafter simply referred to as “Z”) in R a is shown below.
Figure JPOXMLDOC01-appb-C000031
　上記式において、＊は、主鎖のＳｉに結合する部位を意味し、…は、ＺＳｉ以外の所定の基が結合していること、即ち、Ｓｉ原子の３本の結合手がすべて…である場合、ＺＳｉの繰り返しの終了箇所を意味する。また、Ｓｉの右肩の数字は、＊から数えたＺ基を介して直鎖状に連結されたＳｉの出現数を意味する。即ち、Ｓｉ２でＺＳｉ繰り返しが終了している鎖は「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」が２個であり、同様に、Ｓｉ３、Ｓｉ４およびＳｉ５でＺＳｉ繰り返しが終了している鎖は、それぞれ、「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」が３、４および５個である。なお、上記の式から明らかなように、Ｒａ中には、ＺＳｉ鎖が複数存在するが、これらはすべて同じ長さである必要はなく、それぞれ任意の長さであってもよい。 In the above formula, * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition. The number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *. That is, the chain in which ZSi repetition is completed in Si 2 has “the number of Si atoms linearly linked through Z 1 group in R a ”, and similarly, Si 3 , Si The chains in which the ZSi repetition is terminated with 4 and Si 5 have “number of Si atoms connected in a straight chain via the Z 1 group in R a ” being 3, 4 and 5, respectively. As is apparent from the above equation, is in the R a, but ZSi chain there are multiple, they need not be all the same length, each may be of any length.
　好ましい態様において、下記に示すように、「Ｒａ中のＺ１基を介して直鎖状に連結されるＳｉ原子の数」は、すべての鎖において、１個（左式）または２個（右式）である。
Figure JPOXMLDOC01-appb-C000032
 In a preferred embodiment, as shown below, “the number of Si atoms connected linearly via the Z 1 group in R a ” is 1 (left formula) or 2 ( (Right type).
Figure JPOXMLDOC01-appb-C000032
　一の態様において、Ｒａ中のＺ基を介して直鎖状に連結されるＳｉ原子の数は１個または２個、好ましくは１個である。 In one embodiment, the number of Si atoms connected in a straight chain via a Z group in R a is 1 or 2, preferably 1.
　式中、Ｒ７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the formula, R 72 independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
　上記「加水分解可能な基」とは、本明細書において用いられる場合、加水分解反応を受け得る基を意味する。加水分解可能な基の例としては、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝Ｃ（Ｒ）２、－Ｎ（Ｒ）２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）などが挙げられ、好ましくは－ＯＲ（アルコキシ基）である。Ｒの例には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。 The “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
　好ましくは、Ｒ７２は、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 Preferably, R 72 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
　式中、Ｒ７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the formula, R 73 independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｐ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｑ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｒ１は、各出現においてそれぞれ独立して、０～３の整数である。ただし、ｐ１、ｑ１およびｒ１の和は３である。 Wherein p1 is independently an integer of 0 to 3 at each occurrence; q1 is independently an integer of 0 to 3 at each occurrence; and r1 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p1, q1 and r1 is 3.
　好ましい態様において、Ｒａ中の末端のＲａ’（Ｒａ’が存在しない場合、Ｒａ）において、上記ｑ１は、好ましくは２以上、例えば２または３であり、より好ましくは３である。 In a preferred embodiment, '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒａの末端部の少なくとも１つは、－Ｓｉ（－Ｚ１－ＳｉＲ７２ ｑＲ７３ ｒ）２または－Ｓｉ（－Ｚ１－ＳｉＲ７２ ｑＲ７３ ｒ）３、好ましくは－Ｓｉ（－Ｚ１－ＳｉＲ７２ ｑＲ７３ ｒ）３であり得る。式中、（－Ｚ１－ＳｉＲ７２ ｑＲ７３ ｒ）の単位は、好ましくは（－Ｚ１－ＳｉＲ７２ ３）である。さらに好ましい態様において、Ｒａの末端部は、すべて－Ｓｉ（－Ｚ１－ＳｉＲ７２ ｑＲ７３ ｒ）３、好ましくは－Ｓｉ（－Ｚ１－ＳｉＲ７２ ３）３であり得る。 In a preferred embodiment, at least one of the terminal portions of R a is —Si (—Z 1 —SiR 72 q R 73 r ) 2 or —Si (—Z 1 —SiR 72 q R 73 r ) 3 , preferably — Si (—Z 1 —SiR 72 q R 73 r ) 3 Wherein, - the unit of (Z 1 -SiR 72 q R 73 r) is preferably (-Z 1 -SiR 72 3). In a further preferred embodiment, the terminal portions of R a may be all —Si (—Z 1 —SiR 72 q R 73 r ) 3 , preferably —Si (—Z 1 —SiR 72 3 ) 3 .
　上記式（Ｃ１）および（Ｃ２）においては、少なくとも１つのＲ７２が存在する。 In the above formulas (C1) and (C2), at least one R 72 is present.
　上記式中、Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 In the above formula, R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence.
　上記Ｒｂは、好ましくは、水酸基、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝Ｃ（Ｒ）２、－Ｎ（Ｒ）２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）であり、好ましくは－ＯＲである。Ｒは、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。より好ましくは、Ｒｃは、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはメチル基を表す）である。 R b is preferably a hydroxyl group, —OR, —OCOR, —O—N═C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is substituted or unsubstituted) An alkyl group having 1 to 4 carbon atoms), preferably —OR. R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group. More preferably, R c is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
　上記式中、Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the above formula, R c independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｋ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｌ１は、各出現においてそれぞれ独立して、０～３の整数であり；ｍ１は、各出現においてそれぞれ独立して、０～３の整数である。ただし、ｋ１、ｌ１およびｍ１の和は、３である。 Where k1 is independently an integer of 0 to 3 at each occurrence; l1 is independently an integer of 0 to 3 at each occurrence; m1 is independently at each occurrence. And an integer from 0 to 3. However, the sum of k1, l1 and m1 is 3.
　上記式（Ｃ１）および（Ｃ２）で表される化合物は、例えば、Ｒｆ１－ＰＦＰＥ１－部分に対応するパーフルオロポリエーテル誘導体を原料として、末端に水酸基を導入した後、末端に不飽和結合を有する基を導入し、この不飽和結合を有する基とハロゲン原子を有するシリル誘導体とを反応させ、さらにこのシリル基に末端に水酸基を導入し、導入した不飽和結合を有する基とシリル誘導体とを反応させることにより得ることができる。例えば、以下のようにして得ることができる。 The compounds represented by the above formulas (C1) and (C2) are, for example, using a perfluoropolyether derivative corresponding to the Rf 1 -PFPE 1 -moiety as a raw material, introducing a hydroxyl group at the terminal, and then unsaturated bond at the terminal A group having an unsaturated bond, a group having an unsaturated bond and a silyl derivative having a halogen atom are reacted, a hydroxyl group is further introduced into the terminal of the silyl group, and the group having an unsaturated bond and the silyl derivative are introduced. Can be obtained by reacting. For example, it can be obtained as follows.
　好ましい式（Ｃ１）および（Ｃ２）で示される化合物は、下記式（Ｃ１”）および（Ｃ２”）：
Figure JPOXMLDOC01-appb-C000033
 ［式中：
　ＰＦＰＥ１は、それぞれ独立して、式：
　　　　－（ＯＣ４Ｆ８）ａ－（ＯＣ３Ｆ６）ｂ－（ＯＣ２Ｆ４）ｃ－（ＯＣＦ２）ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり； 
　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｘ７は、－ＣＨ２Ｏ（ＣＨ２）２－、－ＣＨ２Ｏ（ＣＨ２）３－または－ＣＨ２Ｏ（ＣＨ２）６－を表し；
　Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ７１ ｐ１Ｒ７２ ｑ１Ｒ７３ ｒ１を表し；
　Ｚ１は、Ｃ１－６アルキレン基を表し；
　Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
　Ｒａ’は、Ｒａと同意義であり；
　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個であり；
　Ｒ７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
　Ｒ７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
　ｐ１は、各出現においてそれぞれ独立して、０～２の整数であり；
　ｑ１は、各出現においてそれぞれ独立して、１～３の整数、好ましくは３であり；
　ｒ１は、各出現においてそれぞれ独立して、０～２の整数であり；
　ただし、一のＲａにおいて、ｐ１、ｑ１およびｒ１の和は３である。］
で表される化合物である。 Preferred compounds represented by the formulas (C1) and (C2) are represented by the following formulas (C1 ″) and (C2 ″):
Figure JPOXMLDOC01-appb-C000033
 [Where:
Each PFPE 1 is independently of the formula:
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
X 7 represents —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 —;
R a independently represents at each occurrence —Z 1 —SiR 71 p1 R 72 q1 R 73 r1 ;
Z 1 represents a C 1-6 alkylene group;
R 71 independently represents R a ′ at each occurrence;
R a ′ is synonymous with R a ;
In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5;
R 72 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
R 73 independently represents at each occurrence a hydrogen atom or a lower alkyl group;
p1 is independently an integer from 0 to 2 at each occurrence;
q1 is independently an integer from 1 to 3, preferably 3 at each occurrence;
r1 is independently an integer from 0 to 2 at each occurrence;
However, in one Ra , the sum of p1, q1, and r1 is 3. ]
It is a compound represented by these.
　上記式（Ｃ１）および（Ｃ２）で表される化合物は、例えば以下のようにして製造することができる。下記式（Ｃ１－４）または（Ｃ２－４）：
Figure JPOXMLDOC01-appb-C000034
 ［式中：
　ＰＦＰＥ１は、それぞれ独立して、式：
　　　　－（ＯＣ４Ｆ８）ａ－（ＯＣ３Ｆ６）ｂ－（ＯＣ２Ｆ４）ｃ－（ＯＣＦ２）ｄ－
（式中、ａ、ｂ、ｃおよびｄは、それぞれ独立して、０～２００の整数であって、ａ、ｂ、ｃおよびｄの和は少なくとも１であり、添字ａ、ｂ、ｃまたはｄを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
で表される基であり；
　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
　Ｘ７’は、それぞれ独立して、単結合または２～１０価の有機基を表し；
　γは、それぞれ独立して、１～９の整数であり；
　γ’は、それぞれ独立して、１～９の整数であり；
　Ｒ９２は、単結合または２価の有機基である。］
で表される化合物を、ＨＳｉＲ９３ ｋ１Ｒｂ ｌ１Ｒｃ ｍ１（式中、Ｒ９３はハロゲン原子、例えばフッ素原子、塩素原子、臭素原子またはヨウ素原子、好ましくは塩素原子であり、Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し、Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し、ｋ１は１～３の整数であり、ｌ１およびｍ１は、それぞれ独立して、０～２の整数であり、ｋ１、ｌ１およびｍ１の和は３である。）で表される化合物と反応させて、式（Ｃ１－５）または（Ｃ２－５）：
Figure JPOXMLDOC01-appb-C000035
 ［式中、Ｒｆ１、ＰＦＰＥ１、Ｒ９２、Ｒ９３、Ｒｂ、Ｒｃ、γ、γ’、Ｘ７’、ｋ１、ｌ１およびｍ１は、上記と同意義である。］
で表される化合物を得る。 The compounds represented by the above formulas (C1) and (C2) can be produced, for example, as follows. The following formula (C1-4) or (C2-4):
Figure JPOXMLDOC01-appb-C000034
 [Where:
Each PFPE 1 is independently of the formula:
-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
Wherein a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d The order of existence of each repeating unit with parentheses attached with is arbitrary in the formula.)
A group represented by:
Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
Each X 7 ′ independently represents a single bond or a divalent to 10-valent organic group;
each γ is independently an integer from 1 to 9;
each γ ′ is independently an integer from 1 to 9;
R 92 is a single bond or a divalent organic group. ]
In a compound represented by, HSiR 93 k1 R b l1 R c m1 ( wherein, R 93 is a halogen atom, such as fluorine atom, chlorine atom, bromine atom or iodine atom, preferably a chlorine atom, R b is Each occurrence independently represents a hydroxyl group or a hydrolyzable group, R c each independently represents a hydrogen atom or a lower alkyl group, each k1 represents an integer of 1 to 3, And m1 are each independently an integer of 0 to 2, and the sum of k1, l1 and m1 is 3.) and is reacted with a compound represented by formula (C1-5) or (C2- 5):
Figure JPOXMLDOC01-appb-C000035
 [Wherein, Rf 1 , PFPE 1 , R 92 , R 93 , R b , R c , γ, γ ′, X 7 ′ , k1, 11 and m1 have the same meanings as described above. ]
To obtain a compound represented by:
　得られた式（Ｃ１－５）または（Ｃ２－５）で表される化合物を、Ｈａｌ－Ｊ－Ｒ８４－ＣＨ＝ＣＨ２（式中、Ｈａｌはハロゲン原子（例えば、Ｉ、Ｂｒ、Ｃｌ、Ｆ等）を表し、Ｊは、Ｍｇ、Ｃｕ、ＰｄまたはＺｎを表し、Ｒ９４は単結合または２価の有機基を表す。）で表される化合物と反応させて、式（Ｃ１－６）または（Ｃ２－６）：
Figure JPOXMLDOC01-appb-C000036
 ［式中、Ｒｆ１、ＰＦＰＥ１、Ｒ９２、Ｒ９４、Ｒｂ、Ｒｃ、γ、γ’、Ｘ７’、ｋ１、ｌ１およびｍ１は、上記と同意義である。］
で表される化合物を得る。 The obtained compound represented by the formula (C1-5) or (C2-5) is converted into Hal-JR 84 —CH═CH 2 (wherein Hal is a halogen atom (eg, I, Br, Cl, F, etc.), J represents Mg, Cu, Pd or Zn, and R 94 represents a single bond or a divalent organic group.) And is reacted with a compound represented by formula (C1-6) Or (C2-6):
Figure JPOXMLDOC01-appb-C000036
 [Wherein, Rf 1 , PFPE 1 , R 92 , R 94 , R b , R c , γ, γ ′, X 7 ′ , k 1, l 1 and m 1 are as defined above. ]
To obtain a compound represented by:
　得られた式（Ｃ１－６）または（Ｃ２－６）で表される化合物を、ＨＳｉＭ３（式中、Ｍは、それぞれ独立して、ハロゲン原子、Ｒ７２またはＲ７３であり、Ｒ７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し、Ｒ７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。）と反応させて、必要に応じて、上記ハロゲン原子を、Ｒ７２またはＲ７３に変換して、式（Ｃ１’’’）または（Ｃ２’’’）：
Figure JPOXMLDOC01-appb-C000037
 ［式中、Ｒｆ１、ＰＦＰＥ１、Ｒ７２、Ｒ７３、Ｒ９２、Ｒ９４、Ｒｂ、Ｒｃ、γ、γ’、Ｘ７’、ｋ１、ｌ１およびｍ１は、上記と同意義であり；
　ｑ１は、各出現においてそれぞれ独立して、１～３の整数であり；
　ｒ１は、各出現においてそれぞれ独立して、０～２の整数である。］
で表される化合物を得ることができる。 The obtained compound represented by the formula (C1-6) or (C2-6) is converted into HSiM 3 (wherein M is independently a halogen atom, R 72 or R 73 , and R 72 is Each independently at each occurrence represents a hydroxyl group or a hydrolyzable group, and R 73 each independently at each occurrence represents a hydrogen atom or a lower alkyl group.) , The halogen atom is converted to R 72 or R 73 to give the formula (C1 ′ ″) or (C2 ′ ″):
Figure JPOXMLDOC01-appb-C000037
 [Wherein, Rf 1 , PFPE 1 , R 72 , R 73 , R 92 , R 94 , R b , R c , γ, γ ′, X 7 ′ , k1, l1 and m1 are as defined above. ;
q1 is independently an integer of 1 to 3 at each occurrence;
r1 is an integer of 0 to 2 independently at each occurrence. ]
Can be obtained.
　式（Ｃ１’’’）または（Ｃ２’’’）において、Ｘ７’からＲ９２－ＣＨ２ＣＨ２－までの部分が、式（Ｃ１）または（Ｃ２）におけるＸ７に対応し、－Ｒ９４－ＣＨ２ＣＨ２－が式（Ｃ１）または（Ｃ２）におけるＺに対応する。 In formula (C1 ′ ″) or (C2 ′ ″), the portion from X 7 ′ to R 92 —CH 2 CH 2 — corresponds to X 7 in formula (C1) or (C2), and —R 94 —CH 2 CH 2 — corresponds to Z in the formula (C1) or (C2).
　式（Ｄ１）および（Ｄ２）：
Figure JPOXMLDOC01-appb-C000038
 Formulas (D1) and (D2):
Figure JPOXMLDOC01-appb-C000038
　上記式（Ｄ１）および（Ｄ２）中、Ｒｆ１およびＰＦＰＥ１は、上記式（Ａ１）および（Ａ２）に関する記載と同意義である。 In the above formulas (D1) and (D2), Rf 1 and PFPE 1 are the same as those described for the above formulas (A1) and (A2).
　上記式中、Ｘ９は、それぞれ独立して、単結合または２～１０価の有機基を表す。当該Ｘは、式（Ｄ１）および（Ｄ２）で表される化合物において、主に撥水性および表面滑り性等を提供するパーフルオロポリエーテル部（即ち、Ｒｆ１－ＰＦＰＥ１部または－ＰＦＰＥ１－部）と、基材との結合能を提供する部（即ち、δを付して括弧でくくられた基）とを連結するリンカーと解される。従って、当該Ｘは、式（Ｄ１）および（Ｄ２）で表される化合物が安定に存在し得るものであれば、いずれの有機基であってもよい。 In the above formulas, X 9 each independently represents a single bond or a divalent to 10-valent organic group. In the compounds represented by formulas (D1) and (D2), X represents a perfluoropolyether moiety (ie, Rf 1 -PFPE 1 part or -PFPE 1- Part) and a part that provides the binding ability to the substrate (that is, a group attached with δ and enclosed in parentheses). Therefore, X may be any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.
　上記式中、δは１～９の整数であり、δ’は１～９の整数である。これらδおよびδ’は、Ｘの価数に応じて変化し得る。式（Ｄ１）においては、δおよびδ’の和は、Ｘの価数と同じである。例えば、Ｘが１０価の有機基である場合、δおよびδ’の和は１０であり、例えばδが９かつδ’が１、δが５かつδ’が５、またはδが１かつδ’が９となり得る。また、Ｘ９が２価の有機基である場合、δおよびδ’は１である。式（Ｄ２）においては、δはＸ９の価数から１を引いた値である。 In the above formula, δ is an integer of 1 to 9, and δ ′ is an integer of 1 to 9. These δ and δ ′ can vary depending on the valence of X. In the formula (D1), the sum of δ and δ ′ is the same as the valence of X. For example, when X is a 10-valent organic group, the sum of δ and δ ′ is 10, for example, δ is 9 and δ ′ is 1, δ is 5 and δ ′ is 5, or δ is 1 and δ ′. Can be nine. In addition, when X 9 is a divalent organic group, δ and δ ′ are 1. In formula (D2), [delta] is a value obtained by subtracting 1 from the valence of X 9.
　上記Ｘ９は、好ましくは２～７価であり、より好ましくは２～４価であり、さらに好ましくは２価の有機基である。 X 9 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
　一の態様において、Ｘ９は２～４価の有機基であり、δは１～３であり、δ’は１である。 In one embodiment, X 9 is a divalent to tetravalent organic group, δ is 1 to 3, and δ ′ is 1.
　別の態様において、Ｘ９は２価の有機基であり、δは１であり、δ’は１である。この場合、式（Ｄ１）および（Ｄ２）は、下記式（Ｄ１’）および（Ｄ２’）で表される。
Figure JPOXMLDOC01-appb-C000039
 In another embodiment, X 9 is a divalent organic group, δ is 1 and δ ′ is 1. In this case, the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
Figure JPOXMLDOC01-appb-C000039
　上記Ｘ９の例としては、特に限定するものではないが、例えば、Ｘ１に関して記載したものと同様のものが挙げられる。 Examples of X 9 are not particularly limited, and examples thereof include those similar to those described with respect to X 1 .
　一の好ましい態様として、Ｘ５は、－Ｘｃ－ＣＯ－ＮＲ１４－Ｘｄ－または－Ｘｃ－ＣＯ－Ｎ（－Ｘｄ－）２で表される基であり得る。ＸｃおよびＸｄは、上記Ｘ１についての記載と同位置である。 In one preferred embodiment, X 5 may be a group represented by —X c —CO—NR 14 —X d — or —X c —CO—N (—X d —) 2 . X c and X d are the same positions as described for X 1 above.
　好ましい具体的なＸ９は、
単結合、
－ＣＨ２Ｏ（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３－、
－ＣＨ２Ｏ（ＣＨ２）６－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
－ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
－ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
－ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
－ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
－ＣＨ２－、
－（ＣＨ２）２－、
－（ＣＨ２）３－、
－（ＣＨ２）４－、
－（ＣＨ２）５－、
－（ＣＨ２）６－、
－ＣＯ－
－ＣＯＮＨ－
－ＣＯＮＨ－ＣＨ２－、
－ＣＯＮＨ－（ＣＨ２）２－、
－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－
－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）６－、
－ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
－ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
－ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
－ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
－Ｓ－（ＣＨ２）３－、
－（ＣＨ２）２Ｓ（ＣＨ２）３－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
－ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－
－Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
－Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
－ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
－ＯＣＨ２－、
－Ｏ（ＣＨ２）３－、
－ＯＣＦＨＣＦ２－、
Figure JPOXMLDOC01-appb-C000040
 などが挙げられる。 Preferred specific X 9 is
Single bond,
—CH 2 O (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 —,
—CH 2 O (CH 2 ) 6 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
-CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
-CH 2 OCF 2 CHFOCF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2- ,
-CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
-CH 2 OCH 2 CHFCF 2 OCF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
-CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
—CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —
—CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—CH 2 —,
—CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
—CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
-CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
—CH 2 —,
-(CH 2 ) 2- ,
-(CH 2 ) 3- ,
- (CH 2) 4 -,
-(CH 2 ) 5- ,
-(CH 2 ) 6- ,
-CO-
-CONH-
-CONH-CH 2- ,
-CONH- (CH 2 ) 2- ,
— (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —
-CONH- (CH 2 ) 3- ,
-CON (CH 3 )-(CH 2 ) 3- ,
—CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
-CONH- (CH 2 ) 6- ,
-CON (CH 3 )-(CH 2 ) 6- ,
—CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
—CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
—CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 3 —,
—CH 2 O—CONH— (CH 2 ) 6 —,
-S- (CH 2 ) 3- ,
-(CH 2 ) 2 S (CH 2 ) 3- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
-CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
—CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —
-C (O) O- (CH 2 ) 3- ,
-C (O) O- (CH 2 ) 6- ,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
—CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
-OCH 2- ,
—O (CH 2 ) 3 —,
-OCHFCF 2- ,
Figure JPOXMLDOC01-appb-C000040
 Etc.
　上記式中、Ｒｄは、各出現においてそれぞれ独立して、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表す。 In the above formula, R d independently represents —Z 2 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
　式中、Ｚ２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表す。 In the formula, Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence.
　上記Ｚ２は、好ましくは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ－Ｏ－（ＣＨ２）ｈ－（式中、ｇは、０～６の整数、例えば１～６の整数であり、ｈは、０～６の整数、例えば１～６の整数である）または、－フェニレン－（ＣＨ２）ｉ－（式中、ｉは、０～６の整数である）であり、より好ましくはＣ１－３アルキレン基である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 Z 2 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH 2 ) i- (where i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　式中、Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表す。Ｒｄ’は、Ｒｄと同意義である。 In the formula, R 81 independently represents R d ′ at each occurrence. R d ′ has the same meaning as R d .
　Ｒｄ中、Ｚ２基を介して直鎖状に連結されるＣは最大で５個である。即ち、上記Ｒｄにおいて、Ｒ８１が少なくとも１つ存在する場合、Ｒｄ中にＺ２基を介して直鎖状に連結されるＣ原子が２個以上存在するが、かかるＺ２基を介して直鎖状に連結されるＣ原子の数は最大で５個である。なお、「Ｒｄ中のＺ２基を介して直鎖状に連結されるＣ原子の数」とは、Ｒｄ中において直鎖状に連結される－Ｚ２－Ｃ－の繰り返し数と等しくなる。これは、式（Ｃ１）および（Ｃ２）におけるＲａに関する記載と同様である。 In R d , the maximum number of C linked in a straight chain via the Z 2 group is 5. That is, in the above R d , when at least one R 81 is present, there are two or more C atoms linearly linked through the Z 2 group in the R d , but through the Z 2 group, The maximum number of C atoms connected in a straight line is five. The phrase "through the Z 2 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 -C- being linearly linked in a R d Become. This is the same as the description regarding R a in the formulas (C1) and (C2).
　好ましい態様において、「Ｒｄ中のＺ２基を介して直鎖状に連結されるＣ原子の数」は、すべての鎖において、１個（左式）または２個（右式）である。 In a preferred embodiment, the “number of C atoms connected in a straight chain via a Z 2 group in R d ” is 1 (left formula) or 2 (right formula) in all chains.
　一の態様において、Ｒｄ中のＺ２基を介して直鎖状に連結されるＣ原子の数は１個または２個、好ましくは１個である。 In one embodiment, the number of C atoms linked in a straight chain via a Z 2 group in R d is 1 or 2, preferably 1.
　式中、Ｒ８２は、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－２ｎを表す。 In the formula, R 82 represents —Y—SiR 85 n2 R 86 3-2n .
　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表す。 Y represents a divalent organic group independently at each occurrence.
　好ましい態様において、Ｙは、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ’－Ｏ－（ＣＨ２）ｈ’－（式中、ｇ’は、０～６の整数、例えば１～６の整数であり、ｈ’は、０～６の整数、例えば１～６の整数である）、または－フェニレン－（ＣＨ２）ｉ’－（式中、ｉ’は、０～６の整数である）である。これらの基は、例えば、フッ素原子、Ｃ１－６アルキル基、Ｃ２－６アルケニル基、およびＣ２－６アルキニル基から選択される１個またはそれ以上の置換基により置換されていてもよい。 In a preferred embodiment, Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 Is an integer, h ′ is an integer from 0 to 6, for example, an integer from 1 to 6, or —phenylene- (CH 2 ) i ′ — (where i ′ is an integer from 0 to 6) ). These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
　一の態様において、Ｙは、Ｃ１－６アルキレン基、－Ｏ－（ＣＨ２）ｈ’－または－フェニレン－（ＣＨ２）ｉ’－であり得る。Ｙが上記の基である場合、光耐性、特に紫外線耐性がより高くなり得る。 In one embodiment, Y can be a C 1-6 alkylene group, —O— (CH 2 ) h ′ — or —phenylene- (CH 2 ) i ′ —. When Y is a group as described above, light resistance, particularly ultraviolet light resistance can be further increased.
　上記Ｒ５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表す。 R 5 represents a hydroxyl group or a hydrolyzable group independently at each occurrence.
　上記「加水分解可能な基」とは、本明細書において用いられる場合、加水分解反応を受け得る基を意味する。加水分解可能な基の例としては、－ＯＲ、－ＯＣＯＲ、－Ｏ－Ｎ＝Ｃ（Ｒ）２、－Ｎ（Ｒ）２、－ＮＨＲ、ハロゲン（これら式中、Ｒは、置換または非置換の炭素数１～４のアルキル基を示す）などが挙げられ、好ましくは－ＯＲ（アルコキシ基）である。Ｒの例には、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基などの非置換アルキル基；クロロメチル基などの置換アルキル基が含まれる。それらの中でも、アルキル基、特に非置換アルキル基が好ましく、メチル基またはエチル基がより好ましい。水酸基は、特に限定されないが、加水分解可能な基が加水分解して生じたものであってよい。 The “hydrolyzable group” as used herein means a group capable of undergoing a hydrolysis reaction. Examples of hydrolyzable groups include —OR, —OCOR, —O—N═C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group). Examples of R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group. Among them, an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable. The hydroxyl group is not particularly limited, but may be a group produced by hydrolysis of a hydrolyzable group.
　好ましくは、Ｒ８５は、－ＯＲ（式中、Ｒは、置換または非置換のＣ１－３アルキル基、より好ましくはエチル基またはメチル基、特にメチル基を表す）である。 Preferably, R 85 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).
　上記Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 R 86 represents a hydrogen atom or a lower alkyl group independently at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、１～３の整数を表し、好ましくは２または３、より好ましくは３である。 n2 independently represents an integer of 1 to 3, preferably 2 or 3, more preferably 3, for each (-Y-SiR 85 n2 R 86 3-n2 ) unit.
　上記Ｒ８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 R 83 represents a hydrogen atom or a lower alkyl group independently at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｒ２は、各出現においてそれぞれ独立して、０～３の整数である。ただし、ｐ２、ｑ２およびｒ２の和は３である。 Where p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p2, q2 and r2 is 3.
　好ましい態様において、Ｒｄ中の末端のＲｄ’（Ｒｄ’が存在しない場合、Ｒｄ）において、上記ｑ２は、好ましくは２以上、例えば２または３であり、より好ましくは３である。 In a preferred embodiment, '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
　好ましい態様において、Ｒｄの末端部の少なくとも１つは、－Ｃ（－Ｙ－ＳｉＲ８５ ｑ２Ｒ８６ ｒ２）２または－Ｃ（－Ｙ－ＳｉＲ８５ ｑ２Ｒ８６ ｒ２）３、好ましくは－Ｃ（－Ｙ－ＳｉＲ８５ ｑ２Ｒ８６ ｒ２）３であり得る。式中、（－Ｙ－ＳｉＲ８５ ｑ２Ｒ８６ ｒ２）の単位は、好ましくは（－Ｙ－ＳｉＲ８５ ３）である。さらに好ましい態様において、Ｒｄの末端部は、すべて－Ｃ（－Ｙ－ＳｉＲ８５ ｑ２Ｒ８６ ｒ２）３、好ましくは－Ｃ（－Ｙ－ＳｉＲ８５ ３）３であり得る。 In a preferred embodiment, at least one of the terminal ends of R d is —C (—Y—SiR 85 q2 R 86 r2 ) 2 or —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C ( may be -Y-SiR 85 q2 R 86 r2 ) 3. Wherein, (- Y-SiR 85 q2 R 86 r2) units is preferably (-Y-SiR 85 3). In a further preferred embodiment, the terminal portions of R d may be all —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C (—Y—SiR 85 3 ) 3 .
　上記式中、Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表す。ここに、Ｙ、Ｒ８５、Ｒ８６およびｎ２は、上記Ｒ８２における記載と同意義である。 In the above formula, R e independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence. Here, Y, R 85 , R 86 and n2 are as defined in R 82 above.
　上記式中、Ｒｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表す。該低級アルキル基は、好ましくは炭素数１～２０のアルキル基、より好ましくは炭素数１～６のアルキル基、さらに好ましくはメチル基である。 In the above formula, R f independently represents a hydrogen atom or a lower alkyl group at each occurrence. The lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
　式中、ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；ｍ２は、各出現においてそれぞれ独立して、０～３の整数である。ただし、ｋ２、ｌ２およびｍ２の和は３である。 Wherein k2 is independently an integer of 0 to 3 at each occurrence; l2 is independently an integer of 0 to 3 at each occurrence; and m2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of k2, l2, and m2 is 3.
　一の態様において、少なくとも１つのｋ２は２または３であり、好ましくは３である。 In one embodiment, at least one k2 is 2 or 3, preferably 3.
　一の態様において、ｋ２は２または３であり、好ましくは３である。 In one embodiment, k2 is 2 or 3, preferably 3.
　一の態様において、ｌ２は２または３であり、好ましくは３である。 In one embodiment, l2 is 2 or 3, preferably 3.
　上記式（Ｄ１）および（Ｄ２）中、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌは２または３である。即ち、式中、少なくとも２つの－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２基が存在する。 In the above formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one l is 2 or 3. That is, there are at least two —Y—SiR 85 n2 R 86 3-n2 groups in the formula.
　式（Ｄ１）または式（Ｄ２）で表されるパーフルオロ（ポリ）エーテル基含有シラン化合物は、公知の方法を組み合わせることにより製造することができる。例えば、Ｘが２価である式（Ｄ１’）で表される化合物は、限定するものではないが、以下のようにして製造することができる。 The perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods. For example, the compound represented by the formula (D1 ′) in which X is divalent is not limited, but can be produced as follows.
　ＨＯ－Ｘ－Ｃ（ＹＯＨ）３（式中、ＸおよびＹは、それぞれ独立して、２価の有機基である。）で表される多価アルコールに、二重結合を含有する基（好ましくはアリル）、およびハロゲン（好ましくはブロモ）を導入して、Ｈａｌ－Ｘ－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ＝ＣＨ２）３（式中、Ｈａｌはハロゲン、例えばＢｒであり、Ｒは二価の有機基、例えばアルキレン基である。）で表される二重結合含有ハロゲン化物を得る。次いで、末端のハロゲンと、ＲＰＦＰＥ－ＯＨ（式中、ＲＰＦＰＥは、パーフルオロポリエーテル基含有基である。）で表されるパーフルオロポリエーテル基含有アルコールとを反応させて、ＲＰＦＰＥ－Ｏ－Ｘ－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ＝ＣＨ２）３を得る。次いで、末端の－ＣＨ＝ＣＨ２と、ＨＳｉＣｌ３およびアルコールまたはＨＳｉＲ８５ ３と反応させて、ＲＰＦＰＥ－Ｏ－Ｘ－Ｃ（Ｙ－Ｏ－Ｒ－ＣＨ２－ＣＨ２－ＳｉＲ８５ ３）３を得ることができる。 A group containing a double bond (preferably a polyhydric alcohol represented by HO—X—C (YOH) 3 (wherein X and Y are each independently a divalent organic group)) Is allyl), and halogen (preferably bromo), and Hal—X—C (Y—O—R—CH═CH 2 ) 3 (where Hal is halogen, eg Br, R is A double bond-containing halide represented by a valent organic group such as an alkylene group. Next, a terminal halogen is reacted with a perfluoropolyether group-containing alcohol represented by R PFPE —OH (wherein R PFPE is a perfluoropolyether group-containing group), and R PFPE − O—X—C (Y—O—R—CH═CH 2 ) 3 is obtained. The terminal —CH═CH 2 is then reacted with HSiCl 3 and alcohol or HSiR 85 3 to give R PFPE —O—X—C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ) 3 Can be obtained.
　上記式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）で表されるパーフルオロ（ポリ）エーテル基含有シラン化合物は、特に限定されるものではないが、５×１０２～１×１０５の数平均分子量を有し得る。上記数平均分子量は、好ましくは１，０００～３０，０００、より好ましくは２，０００～１５，０００、さらに好ましくは３，０００～８，０００であり得る。 The perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) Without limitation, it may have a number average molecular weight of 5 × 10 2 to 1 × 10 5 . The number average molecular weight is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and still more preferably 3,000 to 8,000.
　尚、本発明において、「数平均分子量」は、１９Ｆ－ＮＭＲにより測定される。 In the present invention, the “number average molecular weight” is measured by 19 F-NMR.
　次に、上記式（Ｅ１）で表されるパーフルオロ（ポリ）エーテル変性化合物について説明する。 Next, the perfluoro (poly) ether-modified compound represented by the above formula (E1) will be described.
　上記式中、ＰＦＰＥ２は、上記したＰＦＰＥ１と同様のパーフルオロ（ポリ）エーテル基であり、それぞれ独立して、式：
　　　－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
で表される基である。式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して、０以上１００以下の整数である。好ましくは、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は５以上であり、より好ましくは１０以上、例えば１０以上１００以下である。また、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。 In the above formula, PFPE 2 is a perfluoro (poly) ether group similar to PFPE 1 described above, and each independently represents a formula:
- (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
It is group represented by these. In the formula, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1. Preferably, a, b, c, d, e and f are each independently an integer of 0 or more and 100 or less. Preferably, the sum of a, b, c, d, e and f is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less. Further, the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula.
　これら繰り返し単位は、直鎖状であっても、分枝鎖状であってもよいが、好ましくは直鎖状である。例えば、－（ＯＣ６Ｆ１２）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ５Ｆ１０）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ（ＣＦ３））－等であってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。また、－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 These repeating units may be linear or branched, but are preferably linear. For example,-(OC 6 F 12 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 ) CF 2 ) — , — (OCF 2 CF 2 CF 2 CF 2 CF (CF 3 )) — or the like may be used, but — (OCF 2 CF 2 CF 2 CF 2 CF 2 CF 2 ) — is preferred. -(OC 5 F 10 )-is-(OCF 2 CF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF 2 CF (CF 3 ) CF 2 ) —, — (OCF 2 CF 2 CF 2 CF (CF 3 )) — and the like are preferable, but — ( OCF 2 CF 2 CF 2 CF 2 CF 2 ) —. -(OC 4 F 8 )-is-(OCF 2 CF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 CF 2 )-,-(OCF 2 CF (CF 3 ) CF 2 )- ,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF ( CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably-(OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —. In addition, — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
　一の態様において、上記ＰＦＰＥ２は、－（ＯＣ３Ｆ６）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。好ましくは、ＰＦＰＥ２は、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）または－（ＯＣＦ（ＣＦ３）ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。より好ましくは、ＰＦＰＥ２は、－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（式中、ｄは１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数である）である。 In one embodiment, the PFPE 2 is — (OC 3 F 6 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there. Preferably, PFPE 2 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). More preferably, PFPE 2 is — (OCF 2 CF 2 CF 2 ) d — (wherein d is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200). is there.
　別の態様において、ＰＦＰＥ２は、－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｃおよびｄは、それぞれ独立して０以上３０以下の整数であり、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）である。、好ましくは、ＰＦＰＥ２は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ｃ－（ＯＣＦ２ＣＦ２ＣＦ２）ｄ－（ＯＣＦ２ＣＦ２）ｅ－（ＯＣＦ２）ｆ－である。一の態様において、ＰＦＰＥ２は、－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－（式中、ｅおよびｆは、それぞれ独立して１以上２００以下、好ましくは５以上２００以下、より好ましくは１０以上２００以下の整数であり、添字ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である）であってもよい。 In another embodiment, PFPE 2 is-(OC 4 F 8 ) c- (OC 3 F 6 ) d- (OC 2 F 4 ) e- (OCF 2 ) f-where c and d are each Each independently represents an integer of 0 or more and 30 or less, and e and f are each independently an integer of 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably 10 or more and 200 or less, and subscripts c, d, The order of presence of each repeating unit in parentheses attached with e or f is arbitrary in the formula). Preferably, PFPE 2 is — (OCF 2 CF 2 CF 2 CF 2 ) c — (OCF 2 CF 2 CF 2 ) d — (OCF 2 CF 2 ) e — (OCF 2 ) f —. In one embodiment, PFPE 2 is — (OC 2 F 4 ) e — (OCF 2 ) f — (wherein e and f are each independently from 1 to 200, preferably from 5 to 200, Preferably, it is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit with the subscript e or f and enclosed in parentheses is arbitrary in the formula).
　さらに別の態様において、ＰＦＰＥ２は、－（Ｒ６－Ｒ７）ｑ－で表される基である。式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり、好ましくはＯＣ２Ｆ４である。式中、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。好ましくは、Ｒ７は、ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせである。ＯＣ２Ｆ４、ＯＣ３Ｆ６およびＯＣ４Ｆ８から独立して選択される２または３つの基の組み合わせとしては、特に限定されないが、例えば－ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ４Ｆ８－、－ＯＣ４Ｆ８ＯＣ３Ｆ６－、－ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ２Ｆ４ＯＣ４Ｆ８－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ２Ｆ４－、－ＯＣ２Ｆ４ＯＣ３Ｆ６ＯＣ３Ｆ６－、－ＯＣ２Ｆ４ＯＣ４Ｆ８ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ２Ｆ４－、－ＯＣ３Ｆ６ＯＣ２Ｆ４ＯＣ３Ｆ６－、－ＯＣ３Ｆ６ＯＣ３Ｆ６ＯＣ２Ｆ４－、および－ＯＣ４Ｆ８ＯＣ２Ｆ４ＯＣ２Ｆ４－等が挙げられる。上記ｑは、２～１００の整数、好ましくは２～５０の整数である。上記式中、ＯＣ２Ｆ４、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２は、直鎖または分枝鎖のいずれであってもよく、好ましくは直鎖である。この態様において、ＰＦＰＥ２は、好ましくは、－（ＯＣ２Ｆ４－ＯＣ３Ｆ６）ｑ－または－（ＯＣ２Ｆ４－ＯＣ４Ｆ８）ｑ－である。 In yet another embodiment, PFPE 2 is a group represented by — (R 6 —R 7 ) q —. In the formula, R 6 is OCF 2 or OC 2 F 4 , preferably OC 2 F 4 . In which R 7 is a group selected from OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or is independently selected from these groups Is a combination of 2 or 3 groups. Preferably, R 7 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups is there. The combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited. For example, —OC 2 F 4 OC 3 F 6 —, —OC 2 F 4 OC 4 F 8 - , - OC 3 F 6 OC 2 F 4 -, - OC 3 F 6 OC 3 F 6 -, - OC 3 F 6 OC 4 F 8 -, - OC 4 F 8 OC 4 F 8 -, - OC 4 F 8 OC 3 F 6 -, - OC 4 F 8 OC 2 F 4 -, - OC 2 F 4 OC 2 F 4 OC 3 F 6 -, - OC 2 F 4 OC 2 F 4 OC 4 F 8 -, - OC 2 F 4 OC 3 F 6 OC 2 F 4 -, - OC 2 F 4 OC 3 F 6 OC 3 F 6 -, - OC 2 F 4 OC 4 F 8 OC 2 F 4 -, -OC 3 F 6 OC 2 F 4 OC 2 F 4 -, - OC 3 F 6 OC 2 F 4 OC 3 F 6 —, —OC 3 F 6 OC 3 F 6 OC 2 F 4 —, —OC 4 F 8 OC 2 F 4 OC 2 F 4 — and the like can be mentioned. Q is an integer of 2 to 100, preferably an integer of 2 to 50. In the above formula, OC 2 F 4 , OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 may be either linear or branched, preferably linear. . In this embodiment, PFPE 2 is preferably — (OC 2 F 4 —OC 3 F 6 ) q — or — (OC 2 F 4 —OC 4 F 8 ) q —.
　上記式中、Ｒｆ２は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表す。 In the above formula, Rf 2 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
　上記１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基における「炭素数１～１６のアルキル基」は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のアルキル基であり、より好ましくは直鎖の炭素数１～３のアルキル基である。 The “alkyl group having 1 to 16 carbon atoms” in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
　上記Ｒｆ２は、好ましくは、１個またはそれ以上のフッ素原子により置換されている炭素数１～１６のアルキル基であり、より好ましくはＣＦ２Ｈ－Ｃ１－１５フルオロアルキレン基であり、さらに好ましくは炭素数１～１６のパーフルオロアルキル基である。 Rf 2 is preferably a C 1-16 alkyl group substituted with one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group, A perfluoroalkyl group having 1 to 16 carbon atoms is preferred.
　該炭素数１～１６のパーフルオロアルキル基は、直鎖であっても、分枝鎖であってもよく、好ましくは、直鎖または分枝鎖の炭素数１～６、特に炭素数１～３のパーフルオロアルキル基であり、より好ましくは直鎖の炭素数１～３のパーフルオロアルキル基、具体的には－ＣＦ３、－ＣＦ２ＣＦ３、または－ＣＦ２ＣＦ２ＣＦ３である。 The perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
　上記式中、Ｚ２は、単結合または２価の有機基を表す。 In the above formula, Z 2 represents a single bond or a divalent organic group.
　上記Ｚ２における２価の有機基は、好ましくは、
－（ＣＲ１８ ２）ｋ７－（Ｏ）ｋ８－（ＮＲ１９）ｋ９－、
［式中：
　Ｒ１８は、それぞれ独立して、水素原子またはフッ素原子であり；
　Ｒ１９は、それぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基を表し；
　ｋ７は、１～２０の整数であり；
　ｋ８は、０～１０の整数であり；
　ｋ９は、０～１０の整数であり；
　ここに、ｋ７、ｋ８またはｋ９を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
である。 The divalent organic group in Z 2 is preferably
-(CR 18 2 ) k7- (O) k8- (NR 19 ) k9- ,
[Where:
Each R 18 is independently a hydrogen atom or a fluorine atom;
R 19 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
k7 is an integer from 1 to 20;
k8 is an integer from 0 to 10;
k9 is an integer from 0 to 10;
Here, k7, k8 or k9 is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ]
It is.
　好ましいＺ２は、
－（ＣＦ２）ｋ７’－または－（ＣＦ２）ｋ７’－（Ｏ）ｋ８’－
［式中：
　ｋ７’は、１～６の整数であり；
　ｋ８’は、１～３の整数であり；
　ここに、ｋ７’またはｋ８’を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
である。 Preferred Z 2 is
-(CF 2 ) k7 ' -or-(CF 2 ) k7' -(O) k8 ' -
[Where:
k7 ′ is an integer from 1 to 6;
k8 ′ is an integer from 1 to 3;
Here, k7 ′ or k8 ′ is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ]
It is.
　上記式中、ｘは１または２であり、ｘが１である場合、Ａは、－ＣＯＯＲ３、－ＰＯ（ＯＲ３）２、－ＳＯ２（ＯＲ３）、または－ＳＯ（ＯＲ３）であり、ｘが２である場合、Ａは、－ＰＯ（ＯＲ３）－である。尚、ｘが２である場合、２つのＲｆ２－ＰＦＰＥ２は、同じであっても異なっていてもよい。 In the above formula, x is 1 or 2, and when x is 1, A is —COOR 3 , —PO (OR 3 ) 2 , —SO 2 (OR 3 ), or —SO (OR 3 ). Yes, when x is 2, A is —PO (OR 3 ) —. When x is 2, the two Rf 2 -PFPE 2 may be the same or different.
　上記式中、Ｒ３は、水素原子または炭化水素基である。 In the above formula, R 3 is a hydrogen atom or a hydrocarbon group.
　上記炭化水素基としては、好ましくは、炭素数１～６アルキル基、好ましくは炭素数１～３のアルキル基、より好ましくはメチル基であり得る。 The hydrocarbon group is preferably an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
　好ましい態様において、ｘは１であり、Ａは、－ＣＯＯＲ３である。 In a preferred embodiment, x is 1 and A is —COOR 3 .
　一の好ましい態様において、ｘは１であり、Ａは、－ＣＯＯＨである。 In one preferred embodiment, x is 1 and A is —COOH.
　別の好ましい態様において、ｘは１であり、Ａは、－ＣＯＯＣＨ３である。 In another preferred embodiment, x is 1 and A is —COOCH 3 .
　上記式（Ｅ１）で表されるパーフルオロ（ポリ）エーテル変性化合物は、上記パーフルオロ（ポリ）エーテル基含有シラン化合物を合成する際の原料化合物の未反応物であってもよいし、別途添加した化合物であってもよい。別途添加する化合物は、合成に用いた化合物と同じ化合物であってもよいし、異なる化合物であってもよい。 The perfluoro (poly) ether-modified compound represented by the above formula (E1) may be an unreacted raw material compound when synthesizing the perfluoro (poly) ether group-containing silane compound, or may be added separately. It may be a compound. The compound added separately may be the same compound as the compound used for the synthesis, or may be a different compound.
　上記式（Ｅ１）で表されるパーフルオロ（ポリ）エーテル変性化合物は、特に限定されるものではないが、５×１０２～１×１０５の数平均分子量を有し得る。上記数平均分子量は、好ましくは１，０００～３０，０００、より好ましくは２，０００～１５，０００、さらに好ましくは３，０００～８，０００であり得る。 The perfluoro (poly) ether-modified compound represented by the above formula (E1) is not particularly limited, but may have a number average molecular weight of 5 × 10 2 to 1 × 10 5 . The number average molecular weight is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, and still more preferably 3,000 to 8,000.
　好ましい態様において、上記式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）または（Ｄ２）で表されるパーフルオロ（ポリ）エーテル基含有シラン化合物の数平均分子量と、式（Ｅ１）で表されるパーフルオロ（ポリ）エーテル変性化合物の数平均分子量の差は、２，０００以内、好ましくは１，５００以内、より好ましくは１，０００以内、さらに好ましくは５００以内である。 In a preferred embodiment, the perfluoro (poly) ether group-containing silane represented by the above formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The difference between the number average molecular weight of the compound and the number average molecular weight of the perfluoro (poly) ether-modified compound represented by the formula (E1) is within 2,000, preferably within 1,500, more preferably within 1,000. More preferably, it is within 500.
　本発明の組成物中、上記パーフルオロ（ポリ）エーテル基含有シラン化合物と上記パーフルオロ（ポリ）エーテル変性化合物の含有量の比は、９９．９９：０．０１～７０：３０、好ましくは９９．５：０．５～８０：２０、より好ましくは９９：１～９０：１０であり得る。かかる範囲とすることで、パーフルオロ（ポリ）エーテル変性化合物は、パーフルオロ（ポリ）エーテル基含有シラン化合物と基材との反応を効率よく触媒することができる。 In the composition of the present invention, the content ratio of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether-modified compound is 99.99: 0.01 to 70:30, preferably 99. .5: 0.5 to 80:20, more preferably 99: 1 to 90:10. By setting it as this range, the perfluoro (poly) ether modified compound can efficiently catalyze the reaction between the perfluoro (poly) ether group-containing silane compound and the substrate.
　一の態様において、本発明の組成物中の上記パーフルオロ（ポリ）エーテル基含有シラン化合物と上記パーフルオロ（ポリ）エーテル変性化合物の含有量の比は、９９．９９：０．０１～９７：３、好ましくは９９．９：０．１～９８：２であり得る。別の態様において、本発明の組成物中の上記パーフルオロ（ポリ）エーテル基含有シラン化合物と上記パーフルオロ（ポリ）エーテル変性化合物の含有量の比は、９５：５～７０：３０、好ましくは９２：８～８０：２０であり得る。 In one embodiment, the ratio of the content of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether-modified compound in the composition of the present invention is 99.99: 0.01 to 97: 3, preferably 99.9: 0.1 to 98: 2. In another embodiment, the ratio of the content of the perfluoro (poly) ether group-containing silane compound to the perfluoro (poly) ether-modified compound in the composition of the present invention is 95: 5 to 70:30, preferably 92: 8 to 80:20.
　本発明の組成物は、上記パーフルオロ（ポリ）エーテル基含有シラン化合物および上記パーフルオロ（ポリ）エーテル変性化合物に加え、他の成分を含んでいてもよい。かかる他の成分としては、特に限定されるものではないが、例えば、他の表面処理化合物、含フッ素オイルとして理解され得る（非反応性の）フルオロポリエーテル化合物、好ましくはパーフルオロ（ポリ）エーテル化合物（以下、「含フッ素オイル」と言う）、シリコーンオイルとして理解され得る（非反応性の）シリコーン化合物（以下、「シリコーンオイル」と言う）、触媒などが挙げられる。 The composition of the present invention may contain other components in addition to the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound. Such other components are not particularly limited. For example, other surface treatment compounds, (non-reactive) fluoropolyether compounds that can be understood as fluorine-containing oils, preferably perfluoro (poly) ethers. Examples thereof include a compound (hereinafter referred to as “fluorinated oil”), a silicone compound (hereinafter referred to as “silicone oil”) that can be understood as a silicone oil (hereinafter referred to as “silicone oil”), a catalyst, and the like.
　上記含フッ素オイルとしては、特に限定されるものではないが、例えば、以下の一般式（３）で表される化合物（パーフルオロ（ポリ）エーテル化合物）が挙げられる。
　Ｒｆ５－（ＯＣ４Ｆ８）ａ’－（ＯＣ３Ｆ６）ｂ’－（ＯＣ２Ｆ４）ｃ’－（ＯＣＦ２）ｄ’－Ｒｆ６　　　・・・（３）
　式中、Ｒｆ５は、１個またはそれ以上のフッ素原子により置換されていてもよいＣ１－１６のアルキル基（好ましくは、Ｃ１―１６のパーフルオロアルキル基）を表し、Ｒｆ６は、１個またはそれ以上のフッ素原子により置換されていてもよいＣ１－１６のアルキル基（好ましくは、Ｃ１－１６のパーフルオロアルキル基）、フッ素原子または水素原子を表し、Ｒｆ５およびＲｆ６は、より好ましくは、それぞれ独立して、Ｃ１－３のパーフルオロアルキル基である。
　ａ’、ｂ’、ｃ’およびｄ’は、ポリマーの主骨格を構成するパーフルオロ（ポリ）エーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上３００以下の整数であって、ａ’、ｂ’、ｃ’およびｄ’の和は少なくとも１、好ましくは１～３００、より好ましくは２０～３００である。添字ａ’、ｂ’、ｃ’またはｄ’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。これら繰り返し単位のうち、－（ＯＣ４Ｆ８）－は、－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２ＣＦ２）－、－（ＯＣＦ２ＣＦ（ＣＦ３）ＣＦ２）－、－（ＯＣＦ２ＣＦ２ＣＦ（ＣＦ３））－、－（ＯＣ（ＣＦ３）２ＣＦ２）－、－（ＯＣＦ２Ｃ（ＣＦ３）２）－、－（ＯＣＦ（ＣＦ３）ＣＦ（ＣＦ３））－、－（ＯＣＦ（Ｃ２Ｆ５）ＣＦ２）－および－（ＯＣＦ２ＣＦ（Ｃ２Ｆ５））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ３Ｆ６）－は、－（ＯＣＦ２ＣＦ２ＣＦ２）－、－（ＯＣＦ（ＣＦ３）ＣＦ２）－および－（ＯＣＦ２ＣＦ（ＣＦ３））－のいずれであってもよく、好ましくは－（ＯＣＦ２ＣＦ２ＣＦ２）－である。－（ＯＣ２Ｆ４）－は、－（ＯＣＦ２ＣＦ２）－および－（ＯＣＦ（ＣＦ３））－のいずれであってもよいが、好ましくは－（ＯＣＦ２ＣＦ２）－である。 Although it does not specifically limit as said fluorine-containing oil, For example, the compound (perfluoro (poly) ether compound) represented by the following General formula (3) is mentioned.
Rf 5- (OC 4 F 8 ) a ' -(OC 3 F 6 ) b' -(OC 2 F 4 ) c ' -(OCF 2 ) d' -Rf 6 (3)
In the formula, Rf 5 represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, and Rf 6 represents Represents a C 1-16 alkyl group (preferably a C 1-16 perfluoroalkyl group) optionally substituted by one or more fluorine atoms, a fluorine atom or a hydrogen atom, Rf 5 and Rf 6 Are more preferably each independently a C 1-3 perfluoroalkyl group.
a ′, b ′, c ′ and d ′ each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, and are each independently an integer of 0 to 300, , A ′, b ′, c ′ and d ′ are at least 1, preferably 1 to 300, more preferably 20 to 300. The order of presence of each repeating unit in parentheses with subscripts a ′, b ′, c ′ or d ′ is arbitrary in the formula. Among these repeating units, — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —. -(OC 3 F 6 )-is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Of these, — (OCF 2 CF 2 CF 2 ) — is preferable. — (OC 2 F 4 ) — may be either — (OCF 2 CF 2 ) — or — (OCF (CF 3 )) —, but is preferably — (OCF 2 CF 2 ) —.
　上記一般式（３）で表されるパーフルオロ（ポリ）エーテル化合物の例として、以下の一般式（３ａ）および（３ｂ）のいずれかで示される化合物（１種または２種以上の混合物であってよい）が挙げられる。
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－Ｒｆ６　　　　　　　　　・・・（３ａ）
　Ｒｆ５－（ＯＣＦ２ＣＦ２ＣＦ２ＣＦ２）ａ’’－（ＯＣＦ２ＣＦ２ＣＦ２）ｂ’’－（ＯＣＦ２ＣＦ２）ｃ’’－（ＯＣＦ２）ｄ’’－Ｒｆ６　　　　　　　・・・（３ｂ）
　これら式中、Ｒｆ５およびＲｆ６は上記の通りであり；式（３ａ）において、ｂ’’は１以上１００以下の整数であり；式（３ｂ）において、ａ’’およびｂ’’は、それぞれ独立して１以上３０以下の整数であり、ｃ’’およびｄ’’はそれぞれ独立して１以上３００以下の整数である。添字ａ’’、ｂ’’、ｃ’’、ｄ’’を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。 As an example of the perfluoro (poly) ether compound represented by the general formula (3), a compound represented by any one of the following general formulas (3a) and (3b) (one kind or a mixture of two or more kinds) may be used. May be included).
Rf 5- (OCF 2 CF 2 CF 2 ) b '' -Rf 6 (3a)
Rf 5 — (OCF 2 CF 2 CF 2 CF 2 ) a ″ — (OCF 2 CF 2 CF 2 ) b ″ — (OCF 2 CF 2 ) c ″ — (OCF 2 ) d ″ —Rf 6. .. (3b)
In these formulas, Rf 5 and Rf 6 are as described above; in formula (3a), b ″ is an integer of 1 to 100; in formula (3b), a ″ and b ″ are Each independently represents an integer of 1 to 30, and c ″ and d ″ are each independently an integer of 1 to 300. The order of existence of each repeating unit with subscripts a ″, b ″, c ″, d ″ and parentheses is arbitrary in the formula.
　上記含フッ素オイルは、１，０００～３０，０００の平均分子量を有していてよい。これにより、高い表面滑り性を得ることができる。 The fluorine-containing oil may have an average molecular weight of 1,000 to 30,000. Thereby, high surface slipperiness can be obtained.
　本発明の組成物中、含フッ素オイルは、上記パーフルオロ（ポリ）エーテル基含有シラン化合物および上記のパーフルオロ（ポリ）エーテル変性化合物の合計１００質量部（それぞれ、２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～５００質量部、好ましくは０～４００質量部、より好ましくは５～３００質量部で含まれ得る。 In the composition of the present invention, the fluorine-containing oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound. For example, 0 to 500 parts by mass, preferably 0 to 400 parts by mass, more preferably 5 to 300 parts by mass.
　一般式（３ａ）で示される化合物および一般式（３ｂ）で示される化合物は、それぞれ単独で用いても、組み合わせて用いてもよい。一般式（３ａ）で示される化合物よりも、一般式（３ｂ）で示される化合物を用いるほうが、より高い表面滑り性が得られるので好ましい。これらを組み合わせて用いる場合、一般式（３ａ）で表される化合物と、一般式（３ｂ）で表される化合物との質量比は、１：１～１：３０が好ましく、１：１～１：１０がより好ましい。かかる質量比によれば、表面滑り性と摩擦耐久性のバランスに優れた表面処理層を得ることができる。 The compound represented by the general formula (3a) and the compound represented by the general formula (3b) may be used alone or in combination. It is preferable to use the compound represented by the general formula (3b) rather than the compound represented by the general formula (3a) because higher surface slip properties can be obtained. When these are used in combination, the mass ratio of the compound represented by the general formula (3a) and the compound represented by the general formula (3b) is preferably 1: 1 to 1:30, and preferably 1: 1 to 1 : 10 is more preferable. According to such a mass ratio, a surface treatment layer having an excellent balance between surface slipperiness and friction durability can be obtained.
　一の態様において、含フッ素オイルは、一般式（３ｂ）で表される１種またはそれ以上の化合物を含む。かかる態様において、表面処理剤中の上記パーフルオロ（ポリ）エーテル基含有シラン化合物および上記のパーフルオロ（ポリ）エーテル変性化合物の合計と、式（３ｂ）で表される化合物との質量比は、４：１～１：４であることが好ましい。 In one embodiment, the fluorine-containing oil contains one or more compounds represented by the general formula (3b). In such an aspect, the mass ratio of the sum of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound in the surface treatment agent to the compound represented by formula (3b) is: It is preferably 4: 1 to 1: 4.
　好ましい態様において、真空蒸着法により表面処理層を形成する場合には、上記パーフルオロ（ポリ）エーテル基含有シラン化合物および上記のパーフルオロ（ポリ）エーテル変性化合物の平均分子量よりも、含フッ素オイルの平均分子量を大きくしてもよい。このような平均分子量とすることにより、より優れた摩擦耐久性と表面滑り性を得ることができる。 In a preferred embodiment, when the surface treatment layer is formed by a vacuum vapor deposition method, the fluorine-containing oil has a higher molecular weight than the average molecular weight of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound. The average molecular weight may be increased. By setting such an average molecular weight, more excellent friction durability and surface slipperiness can be obtained.
　また、別の観点から、含フッ素オイルは、一般式Ｒｆ’－Ｆ（式中、Ｒｆ’はＣ５－１６パーフルオロアルキル基である。）で表される化合物であってよい。また、クロロトリフルオロエチレンオリゴマーであってもよい。Ｒｆ’－Ｆで表される化合物およびクロロトリフルオロエチレンオリゴマーは、Ｒｆ１がＣ１－１６パーフルオロアルキル基である上記パーフルオロ（ポリ）エーテル基含有シラン化合物と高い親和性が得られる点で好ましい。 From another viewpoint, the fluorine-containing oil may be a compound represented by the general formula Rf′-F (wherein Rf ′ is a C 5-16 perfluoroalkyl group). Moreover, a chlorotrifluoroethylene oligomer may be sufficient. The compound represented by Rf′-F and the chlorotrifluoroethylene oligomer have a high affinity with the perfluoro (poly) ether group-containing silane compound in which Rf 1 is a C 1-16 perfluoroalkyl group. preferable.
　含フッ素オイルは、表面処理層の表面滑り性を向上させるのに寄与する。 Fluorine-containing oil contributes to improving the surface slipperiness of the surface treatment layer.
　上記シリコーンオイルとしては、例えばシロキサン結合が２，０００以下の直鎖状または環状のシリコーンオイルを用い得る。直鎖状のシリコーンオイルは、いわゆるストレートシリコーンオイルおよび変性シリコーンオイルであってよい。ストレートシリコーンオイルとしては、ジメチルシリコーンオイル、メチルフェニルシリコーンオイル、メチルハイドロジェンシリコーンオイルが挙げられる。変性シリコーンオイルとしては、ストレートシリコーンオイルを、アルキル、アラルキル、ポリエーテル、高級脂肪酸エステル、フルオロアルキル、アミノ、エポキシ、カルボキシル、アルコールなどにより変性したものが挙げられる。環状のシリコーンオイルは、例えば環状ジメチルシロキサンオイルなどが挙げられる。 As the silicone oil, for example, a linear or cyclic silicone oil having a siloxane bond of 2,000 or less can be used. The linear silicone oil may be so-called straight silicone oil and modified silicone oil. Examples of the straight silicone oil include dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil. Examples of the modified silicone oil include those obtained by modifying straight silicone oil with alkyl, aralkyl, polyether, higher fatty acid ester, fluoroalkyl, amino, epoxy, carboxyl, alcohol and the like. Examples of the cyclic silicone oil include cyclic dimethylsiloxane oil.
　本発明の組成物中、かかるシリコーンオイルは、上記パーフルオロ（ポリ）エーテル基含有シラン化合物および上記パーフルオロ（ポリ）エーテル変性化合物の合計１００質量部（２種以上の場合にはこれらの合計、以下も同様）に対して、例えば０～３００質量部、好ましくは０～２００質量部で含まれ得る。 In the composition of the present invention, the silicone oil is a total of 100 parts by mass of the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether-modified compound (in the case of two or more types, the total of these, For example, 0 to 300 parts by mass, preferably 0 to 200 parts by mass may be included.
　シリコーンオイルは、表面処理層の表面滑り性を向上させるのに寄与する。 Silicone oil contributes to improving the surface slipperiness of the surface treatment layer.
　上記触媒としては、酸（例えば酢酸、トリフルオロ酢酸等）、塩基（例えばアンモニア、トリエチルアミン、ジエチルアミン等）、遷移金属（例えばＴｉ、Ｎｉ、Ｓｎ等）等が挙げられる。 Examples of the catalyst include acids (eg, acetic acid, trifluoroacetic acid, etc.), bases (eg, ammonia, triethylamine, diethylamine, etc.), transition metals (eg, Ti, Ni, Sn, etc.), and the like.
　触媒は、上記パーフルオロ（ポリ）エーテル基含有シラン化合物の加水分解および脱水縮合を促進し、表面処理層の形成を促進する。 The catalyst promotes the hydrolysis and dehydration condensation of the perfluoro (poly) ether group-containing silane compound and promotes the formation of the surface treatment layer.
　本発明の組成物は、１つの溶液（または懸濁液もしくは分散液）の形態であってもよく、あるいは、別個の上記パーフルオロ（ポリ）エーテル基含有シラン化合物と上記パーフルオロ（ポリ）エーテル変性化合物の溶液とを使用直前に混合する形態であってもよい。 The composition of the present invention may be in the form of one solution (or suspension or dispersion), or separate the perfluoro (poly) ether group-containing silane compound and the perfluoro (poly) ether. The modified compound solution may be mixed immediately before use.
　本発明の組成物は、多孔質物質、例えば多孔質のセラミック材料、金属繊維、例えばスチールウールを綿状に固めたものに含浸させて、ペレットとすることができる。当該ペレットは、例えば、真空蒸着に用いることができる。 The composition of the present invention can be made into a pellet by impregnating a porous material such as a porous ceramic material or metal fiber such as steel wool hardened in a cotton form. The pellet can be used for, for example, vacuum deposition.
　本発明の組成物は、撥水性、撥油性、防汚性、防水性および高い摩擦耐久性を基材に対して付与することができることから、表面処理剤として好適に使用される。具体的には、本発明の組成物は、特に限定されるものではないが、防汚性コーティング剤または防水性コーティング剤として好適に使用され得る。 The composition of the present invention can be suitably used as a surface treating agent because it can impart water repellency, oil repellency, antifouling property, waterproofness and high friction durability to a substrate. Specifically, the composition of the present invention is not particularly limited, but can be suitably used as an antifouling coating agent or a waterproof coating agent.
　次に、本発明の物品について説明する。 Next, the article of the present invention will be described.
　本発明の物品は、基材と、該基材の表面に本発明の組成物より形成された層（表面処理層）とを含む。この物品は、例えば以下のようにして製造できる。 The article of the present invention includes a base material and a layer (surface treatment layer) formed on the surface of the base material from the composition of the present invention. This article can be manufactured, for example, as follows.
　まず、基材を準備する。本発明に使用可能な基材は、例えばガラス、サファイアガラス、樹脂（天然または合成樹脂、例えば一般的なプラスチック材料であってよく、板状、フィルム、その他の形態であってよい）、金属（アルミニウム、銅、鉄等の金属単体または合金等の複合体であってよい）、セラミックス、半導体（シリコン、ゲルマニウム等）、繊維（織物、不織布等）、毛皮、皮革、木材、陶磁器、石材等、建築部材等、任意の適切な材料で構成され得る。 First, prepare the base material. Substrates that can be used in the present invention include, for example, glass, sapphire glass, resin (natural or synthetic resin, such as a general plastic material, and may be a plate, film, or other form), metal ( It may be a single metal such as aluminum, copper, iron or a composite of an alloy, etc.), ceramics, semiconductor (silicon, germanium, etc.), fiber (woven fabric, non-woven fabric, etc.), fur, leather, wood, ceramics, stone, etc. It can be composed of any suitable material, such as a building member.
　上記ガラスとしては、ソーダライムガラス、アルカリアルミノケイ酸塩ガラス、ホウ珪酸ガラス、無アルカリガラス、クリスタルガラス、石英ガラスが好ましく、化学強化したソーダライムガラス、化学強化したアルカリアルミノケイ酸塩ガラス、および化学結合したホウ珪酸ガラスが特に好ましい。
　樹脂としては、アクリル樹脂、ポリカーボネートが好ましい。 As the glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass, and quartz glass are preferable, chemically strengthened soda lime glass, chemically strengthened alkali aluminosilicate glass, and chemical bond Particularly preferred is borosilicate glass.
As the resin, acrylic resin and polycarbonate are preferable.
　例えば、製造すべき物品が光学部材である場合、基材の表面を構成する材料は、光学部材用材料、例えばガラスまたは透明プラスチックなどであってよい。また、製造すべき物品が光学部材である場合、基材の表面（最外層）に何らかの層（または膜）、例えばハードコート層や反射防止層などが形成されていてもよい。反射防止層には、単層反射防止層および多層反射防止層のいずれを使用してもよい。反射防止層に使用可能な無機物の例としては、ＳｉＯ２、ＳｉＯ、ＺｒＯ２、ＴｉＯ２、ＴｉＯ、Ｔｉ２Ｏ３、Ｔｉ２Ｏ５、Ａｌ２Ｏ３、Ｔａ２Ｏ５、ＣｅＯ２、ＭｇＯ、Ｙ２Ｏ３、ＳｎＯ２、ＭｇＦ２、ＷＯ３などが挙げられる。これらの無機物は、単独で、またはこれらの２種以上を組み合わせて（例えば混合物として）使用してもよい。多層反射防止層とする場合、その最外層にはＳｉＯ２および／またはＳｉＯを用いることが好ましい。製造すべき物品が、タッチパネル用の光学ガラス部品である場合、透明電極、例えば酸化インジウムスズ（ＩＴＯ）や酸化インジウム亜鉛などを用いた薄膜を、基材（ガラス）の表面の一部に有していてもよい。また、基材は、その具体的仕様等に応じて、絶縁層、粘着層、保護層、装飾枠層（Ｉ－ＣＯＮ）、霧化膜層、ハードコーティング膜層、偏光フィルム、相位差フィルム、および液晶表示モジュールなどを有していてもよい。 For example, when the article to be manufactured is an optical member, the material constituting the surface of the substrate may be an optical member material such as glass or transparent plastic. Further, when the article to be manufactured is an optical member, some layer (or film) such as a hard coat layer or an antireflection layer may be formed on the surface (outermost layer) of the substrate. As the antireflection layer, either a single-layer antireflection layer or a multilayer antireflection layer may be used. Examples of inorganic materials that can be used for the antireflection layer include SiO 2 , SiO, ZrO 2 , TiO 2 , TiO, Ti 2 O 3 , Ti 2 O 5 , Al 2 O 3 , Ta 2 O 5 , CeO 2 , MgO. , Y 2 O 3 , SnO 2 , MgF 2 , WO 3 and the like. These inorganic substances may be used alone or in combination of two or more thereof (for example, as a mixture). When a multilayer antireflection layer is used, it is preferable to use SiO 2 and / or SiO for the outermost layer. When the article to be manufactured is an optical glass component for a touch panel, a thin film using a transparent electrode such as indium tin oxide (ITO) or indium zinc oxide is provided on a part of the surface of the substrate (glass). It may be. In addition, the base material is an insulating layer, an adhesive layer, a protective layer, a decorative frame layer (I-CON), an atomized film layer, a hard coating film layer, a polarizing film, a phase difference film, And a liquid crystal display module or the like.
　基材の形状は特に限定されない。また、表面処理層を形成すべき基材の表面領域は、基材表面の少なくとも一部であればよく、製造すべき物品の用途および具体的仕様等に応じて適宜決定され得る。 The shape of the substrate is not particularly limited. In addition, the surface region of the base material on which the surface treatment layer is to be formed may be at least part of the surface of the base material, and can be appropriately determined according to the use and specific specifications of the article to be manufactured.
　かかる基材としては、少なくともその表面部分が、水酸基を元々有する材料から成るものであってよい。かかる材料としては、ガラスが挙げられ、また、表面に自然酸化膜または熱酸化膜が形成される金属（特に卑金属）、セラミックス、半導体等が挙げられる。あるいは、樹脂等のように、水酸基を有していても十分でない場合や、水酸基を元々有していない場合には、基材に何らかの前処理を施すことにより、基材の表面に水酸基を導入したり、増加させたりすることができる。かかる前処理の例としては、プラズマ処理（例えばコロナ放電）や、イオンビーム照射が挙げられる。プラズマ処理は、基材表面に水酸基を導入または増加させ得ると共に、基材表面を清浄化する（異物等を除去する）ためにも好適に利用され得る。また、かかる前処理の別の例としては、炭素－炭素不飽和結合基を有する界面吸着剤をＬＢ法（ラングミュア－ブロジェット法）や化学吸着法等によって、基材表面に予め単分子膜の形態で形成し、その後、酸素や窒素等を含む雰囲気下にて不飽和結合を開裂する方法が挙げられる。 As such a base material, at least a surface portion thereof may be made of a material originally having a hydroxyl group. Examples of such materials include glass, and metals (particularly base metals) on which a natural oxide film or a thermal oxide film is formed on the surface, ceramics, and semiconductors. Alternatively, if it does not suffice if it has hydroxyl groups, such as resin, or if it does not have hydroxyl groups originally, it can be introduced to the surface of the substrate by applying some pretreatment to the substrate. Or increase it. Examples of such pretreatment include plasma treatment (for example, corona discharge) and ion beam irradiation. The plasma treatment can be preferably used for introducing or increasing hydroxyl groups on the surface of the base material and for cleaning the base material surface (removing foreign matter or the like). As another example of such pretreatment, an interfacial adsorbent having a carbon-carbon unsaturated bond group is previously formed on the substrate surface by a monomolecular film by the LB method (Langmuir-Blodgett method) or chemical adsorption method. There is a method of forming in a form and then cleaving the unsaturated bond in an atmosphere containing oxygen, nitrogen or the like.
　またあるいは、かかる基材としては、少なくともその表面部分が、別の反応性基、例えばＳｉ－Ｈ基を１つ以上有するシリコーン化合物や、アルコキシシランを含む材料から成るものであってもよい。 Alternatively, the substrate may be made of a material containing at least a surface portion of a silicone compound having one or more other reactive groups, for example, Si—H groups, or an alkoxysilane.
　次に、かかる基材の表面に、上記の本発明の組成物の膜を形成し、この膜を必要に応じて後処理し、これにより、本発明の組成物から表面処理層を形成する。 Next, a film of the composition of the present invention is formed on the surface of the base material, and the film is post-treated as necessary, thereby forming a surface treatment layer from the composition of the present invention.
　本発明の組成物の膜形成は、本発明の組成物を基材の表面に対して、該表面を被覆するように適用することによって実施できる。被覆方法は、特に限定されない。例えば、湿潤被覆法および乾燥被覆法を使用できる。 The film formation of the composition of the present invention can be carried out by applying the composition of the present invention to the surface of the substrate so as to cover the surface. The coating method is not particularly limited. For example, wet coating methods and dry coating methods can be used.
　湿潤被覆法の例としては、浸漬コーティング、スピンコーティング、フローコーティング、スプレーコーティング、ロールコーティング、グラビアコーティングおよび類似の方法が挙げられる。 Examples of wet coating methods include dip coating, spin coating, flow coating, spray coating, roll coating, gravure coating and similar methods.
　乾燥被覆法の例としては、蒸着（通常、真空蒸着）、スパッタリング、ＣＶＤおよび類似の方法が挙げられる。蒸着法（通常、真空蒸着法）の具体例としては、抵抗加熱、電子ビーム、マイクロ波等を用いた高周波加熱、イオンビームおよび類似の方法が挙げられる。ＣＶＤ方法の具体例としては、プラズマ－ＣＶＤ、光学ＣＶＤ、熱ＣＶＤおよび類似の方法が挙げられる。 Examples of dry coating methods include vapor deposition (usually vacuum vapor deposition), sputtering, CVD, and similar methods. Specific examples of the vapor deposition method (usually vacuum vapor deposition method) include resistance heating, high-frequency heating using an electron beam, microwave, and the like, an ion beam, and similar methods. Specific examples of the CVD method include plasma-CVD, optical CVD, thermal CVD, and similar methods.
　更に、常圧プラズマ法による被覆も可能である。 Furthermore, coating by the atmospheric pressure plasma method is also possible.
　湿潤被覆法を使用する場合、本発明の組成物は、溶媒で希釈されてから基材表面に適用され得る。本発明の組成物の安定性および溶媒の揮発性の観点から、次の溶媒が好ましく使用される：Ｃ５－１２のパーフルオロ脂肪族炭化水素（例えば、パーフルオロヘキサン、パーフルオロメチルシクロヘキサンおよびパーフルオロ－１，３－ジメチルシクロヘキサン）；ポリフルオロ芳香族炭化水素（例えば、ビス（トリフルオロメチル）ベンゼン）；ポリフルオロ脂肪族炭化水素（例えば、Ｃ６Ｆ１３ＣＨ２ＣＨ３（例えば、旭硝子株式会社製のアサヒクリン（登録商標）ＡＣ－６０００）、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン（例えば、日本ゼオン株式会社製のゼオローラ（登録商標）Ｈ）；ハイドロフルオロカーボン（ＨＦＣ）（例えば、１，１，１，３，３－ペンタフルオロブタン（ＨＦＣ－３６５ｍｆｃ））；ハイドロクロロフルオロカーボン（例えば、ＨＣＦＣ－２２５（アサヒクリン（登録商標）ＡＫ２２５））；ヒドロフルオロエーテル（ＨＦＥ）（例えば、パーフルオロプロピルメチルエーテル（Ｃ３Ｆ７ＯＣＨ３）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７０００）、パーフルオロブチルメチルエーテル（Ｃ４Ｆ９ＯＣＨ３）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７１００）、パーフルオロブチルエチルエーテル（Ｃ４Ｆ９ＯＣ２Ｈ５）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７２００）、パーフルオロヘキシルメチルエーテル（Ｃ２Ｆ５ＣＦ（ＯＣＨ３）Ｃ３Ｆ７）（例えば、住友スリーエム株式会社製のＮｏｖｅｃ（商標名）７３００）などのアルキルパーフルオロアルキルエーテル（パーフルオロアルキル基およびアルキル基は直鎖または分枝状であってよい）、あるいはＣＦ３ＣＨ２ＯＣＦ２ＣＨＦ２（例えば、旭硝子株式会社製のアサヒクリン（登録商標）ＡＥ－３０００））、１，２－ジクロロ－１，３，３，３－テトラフルオロ－１－プロペン（例えば、三井・デュポンフロロケミカル社製のバートレル（登録商標）サイオン）など。これらの溶媒は、単独で、または、２種以上を組み合わせて混合物として用いることができる。さらに、例えば、パーフルオロ（ポリ）エーテル基含有シラン化合物およびパーフルオロポリエーテル変性化合物の溶解性を調整する等のために、別の溶媒と混合することもできる。 When using the wet coating method, the composition of the present invention may be diluted with a solvent and then applied to the substrate surface. In view of the stability of the composition of the present invention and the volatility of the solvent, the following solvents are preferably used: C 5-12 perfluoroaliphatic hydrocarbons such as perfluorohexane, perfluoromethylcyclohexane and perfluorohexane. Fluoro-1,3-dimethylcyclohexane); polyfluoroaromatic hydrocarbons (eg, bis (trifluoromethyl) benzene); polyfluoroaliphatic hydrocarbons (eg, C 6 F 13 CH 2 CH 3 (eg, Asahi Glass Corporation) ASAHIKLIN (registered trademark) AC-6000), 1,1,2,2,3,3,4-heptafluorocyclopentane (for example, ZEOLOR (registered trademark) H manufactured by Nippon Zeon Co., Ltd.); Hydro Fluorocarbon (HFC) (for example, 1,1,1,3,3-pentafluorobutane (HFC-365mf )); Hydrochlorofluorocarbon (e.g., HCFC-225 (ASAHIKLIN (TM) AK225)); hydrofluoroether (HFE) (e.g., perfluoropropyl methyl ether (C 3 F 7 OCH 3) ( e.g., Sumitomo Novec (trade name) 7000), perfluorobutyl methyl ether (C 4 F 9 OCH 3 ) (for example, Novec (trade name) 7100 manufactured by Sumitomo 3M Limited), perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) (for example, Novec (trade name) 7200 manufactured by Sumitomo 3M Limited), perfluorohexyl methyl ether (C 2 F 5 CF (OCH 3 ) C 3 F 7 ) (for example, Sumitomo 3M Co., Ltd.) Novec (trade name) 7300 manufactured by the company Alkyl perfluoroalkyl ethers (such as perfluoroalkyl groups and the alkyl group may be straight or branched), or CF 3 CH 2 OCF 2 CHF 2 ( e.g., Asahi Glass ASAHIKLIN Co., Ltd. (registered trademark AE-3000)), 1,2-dichloro-1,3,3,3-tetrafluoro-1-propene (for example, Bertrell (registered trademark) Scion manufactured by Mitsui DuPont Fluorochemicals), etc. These solvents Can be used alone or in combination as a mixture of two or more thereof, for example, for adjusting the solubility of the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether-modified compound. In addition, it can be mixed with another solvent.
　乾燥被覆法を使用する場合、本発明の組成物は、そのまま乾燥被覆法に付してもよく、または、上記した溶媒で希釈してから乾燥被覆法に付してもよい。 When the dry coating method is used, the composition of the present invention may be subjected to the dry coating method as it is, or may be diluted with the above-described solvent and then subjected to the dry coating method.
　膜形成は、膜中で本発明の組成物が、加水分解および脱水縮合のための触媒と共に存在するように実施することが好ましい。簡便には、湿潤被覆法による場合、本発明の組成物を溶媒で希釈した後、基材表面に適用する直前に、本発明の組成物の希釈液に触媒を添加してよい。乾燥被覆法による場合には、触媒添加した本発明の組成物をそのまま蒸着（通常、真空蒸着）処理するか、あるいは鉄や銅などの金属多孔体に、触媒添加した本発明の組成物を含浸させたペレット状物質を用いて蒸着（通常、真空蒸着）処理をしてもよい。 Film formation is preferably carried out so that the composition of the present invention is present together with a catalyst for hydrolysis and dehydration condensation in the film. For convenience, in the case of the wet coating method, after diluting the composition of the present invention with a solvent, the catalyst may be added to the diluted solution of the composition of the present invention immediately before application to the substrate surface. In the case of a dry coating method, the catalyst-added composition of the present invention is directly vapor-deposited (usually vacuum deposition), or a metal porous body such as iron or copper is impregnated with the catalyst-added composition of the present invention. Vapor deposition (usually vacuum deposition) may be performed using the pelletized material.
　触媒には、任意の適切な酸または塩基を使用できる。酸触媒としては、例えば、酢酸、ギ酸、トリフルオロ酢酸などを使用できる。また、塩基触媒としては、例えばアンモニア、有機アミン類などを使用できる。 Any suitable acid or base can be used for the catalyst. As the acid catalyst, for example, acetic acid, formic acid, trifluoroacetic acid and the like can be used. Moreover, as a base catalyst, ammonia, organic amines, etc. can be used, for example.
　次に、必要に応じて、膜を後処理する。この後処理は、特に限定されないが、例えば、水分供給および乾燥加熱を逐次的に実施するものであってよく、より詳細には、以下のようにして実施してよい。 Next, the membrane is post-treated as necessary. Although this post-processing is not specifically limited, For example, a water supply and drying heating may be implemented sequentially, and it may be implemented as follows in detail.
　上記のようにして基材表面に本発明の組成物を膜形成した後、この膜（以下、「前駆体膜」とも言う）に水分を供給する。水分の供給方法は、特に限定されず、例えば、前駆体膜（および基材）と周囲雰囲気との温度差による結露や、水蒸気（スチーム）の吹付けなどの方法を使用してよい。 After the film of the composition of the present invention is formed on the substrate surface as described above, moisture is supplied to this film (hereinafter also referred to as “precursor film”). The method for supplying moisture is not particularly limited, and for example, methods such as dew condensation due to a temperature difference between the precursor film (and the substrate) and the surrounding atmosphere, or spraying of steam (steam) may be used.
　水分の供給は、例えば０～２５０℃、好ましくは６０℃以上、さらに好ましくは１００℃以上とし、好ましくは１８０℃以下、さらに好ましくは１５０℃以下の雰囲気下にて実施し得る。このような温度範囲において水分を供給することにより、加水分解を進行させることが可能である。このときの圧力は特に限定されないが、簡便には常圧とし得る。 The supply of moisture is, for example, 0 to 250 ° C., preferably 60 ° C. or higher, more preferably 100 ° C. or higher, preferably 180 ° C. or lower, more preferably 150 ° C. or lower. By supplying moisture in such a temperature range, hydrolysis can be advanced. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
　次に、該前駆体膜を該基材の表面で、６０℃を超える乾燥雰囲気下にて加熱する。乾燥加熱方法は、特に限定されず、前駆体膜を基材と共に、６０℃を超え、好ましくは１００℃を超える温度であって、例えば２５０℃以下、好ましくは１８０℃以下の温度で、かつ不飽和水蒸気圧の雰囲気下に配置すればよい。このときの圧力は特に限定されないが、簡便には常圧とし得る。 Next, the precursor film is heated on the surface of the substrate in a dry atmosphere exceeding 60 ° C. The drying heating method is not particularly limited, and the temperature of the precursor film together with the base material is higher than 60 ° C., preferably higher than 100 ° C., for example, 250 ° C. or lower, preferably 180 ° C. or lower. What is necessary is just to arrange | position in the atmosphere of saturated water vapor pressure. Although the pressure at this time is not specifically limited, it can be simply a normal pressure.
　このような雰囲気下では、本発明のパーフルオロ（ポリ）エーテル基含有シラン化合物間では、加水分解後のＳｉに結合した基同士が速やかに脱水縮合する。また、かかる化合物と基材との間では、当該化合物の加水分解後のＳｉに結合した基と、基材表面に存在する反応性基との間で速やかに反応し、基材表面に存在する反応性基が水酸基である場合には脱水縮合する。その結果、パーフルオロ（ポリ）エーテル基含有シラン化合物と基材との間で結合が形成される。 In such an atmosphere, groups bonded to Si after hydrolysis rapidly undergo dehydration condensation between the perfluoro (poly) ether group-containing silane compounds of the present invention. Moreover, between such a compound and a base material, it reacts rapidly between the group couple | bonded with Si after the hydrolysis of the said compound, and the reactive group which exists in the base-material surface, and it exists in the base-material surface. When the reactive group is a hydroxyl group, dehydration condensation is performed. As a result, a bond is formed between the perfluoro (poly) ether group-containing silane compound and the substrate.
　上記の水分供給および乾燥加熱は、過熱水蒸気を用いることにより連続的に実施してもよい。 The above water supply and drying heating may be continuously performed by using superheated steam.
　以上のようにして後処理が実施され得る。かかる後処理は、摩擦耐久性を一層向上させるために実施され得るが、本発明の物品を製造するのに必須でないことに留意されたい。例えば、本発明の組成物を基材表面に適用した後、そのまま静置しておくだけでもよい。 Post-processing can be performed as described above. It should be noted that such post-treatment can be performed to further improve friction durability, but is not essential for producing the articles of the present invention. For example, after applying the composition of the present invention to the substrate surface, it may be allowed to stand still.
　上記のようにして、基材の表面に、本発明の組成物の膜に由来する表面処理層が形成され、本発明の物品が製造される。これにより得られる表面処理層は、高い摩擦耐久性を有する。また、この表面処理層は、高い摩擦耐久性に加えて、使用する組成物の組成にもよるが、撥水性、撥油性、防汚性（例えば指紋等の汚れの付着を防止する）、表面滑り性（または潤滑性、例えば指紋等の汚れの拭き取り性や、指に対する優れた触感）などを有し得、機能性薄膜として好適に利用され得る。 As described above, the surface treatment layer derived from the film of the composition of the present invention is formed on the surface of the substrate, and the article of the present invention is manufactured. The surface treatment layer obtained by this has high friction durability. In addition to high friction durability, this surface treatment layer has water repellency, oil repellency, antifouling properties (for example, preventing adhesion of dirt such as fingerprints), surface, etc., depending on the composition of the composition used. It can have slipperiness (or lubricity, for example, the ability to wipe off dirt such as fingerprints, and excellent touch to fingers), and can be suitably used as a functional thin film.
　すなわち本発明はさらに、前記硬化物を最外層に有する光学材料にも関する。 That is, the present invention further relates to an optical material having the cured product as an outermost layer.
　光学材料としては、後記に例示するようなディスプレイ等に関する光学材料のほか、多種多様な光学材料が好ましく挙げられる：例えば、陰極線管（ＣＲＴ；例、ＴＶ、パソコンモニター）、液晶ディスプレイ、プラズマディスプレイ、有機ＥＬディスプレイ、無機薄膜ＥＬドットマトリクスディスプレイ、背面投写型ディスプレイ、蛍光表示管（ＶＦＤ）、電界放出ディスプレイ（ＦＥＤ；Ｆｉｅｌｄ Ｅｍｉｓｓｉｏｎ Ｄｉｓｐｌａｙ）などのディスプレイまたはそれらのディスプレイの保護板、またはそれらの表面に反射防止膜処理を施したもの。 As the optical material, in addition to optical materials relating to displays and the like exemplified below, a wide variety of optical materials are preferably mentioned: for example, cathode ray tube (CRT; eg, TV, personal computer monitor), liquid crystal display, plasma display, Organic EL display, inorganic thin-film EL dot matrix display, rear projection display, fluorescent display tube (VFD), field emission display (FED), or a protective plate of those displays, or reflection on the surface thereof Those with a protective film treatment.
　本発明によって得られる表面処理層を有する物品は、特に限定されるものではないが、光学部材であり得る。光学部材の例には、次のものが挙げられる：眼鏡などのレンズ；ＰＤＰ、ＬＣＤなどのディスプレイの前面保護板、反射防止板、偏光板、アンチグレア板；携帯電話、携帯情報端末などの機器のタッチパネルシート；ブルーレイ（Ｂｌｕ－ｒａｙ（登録商標））ディスク、ＤＶＤディスク、ＣＤ－Ｒ、ＭＯなどの光ディスクのディスク面；光ファイバーなど。 The article having the surface treatment layer obtained by the present invention is not particularly limited, but may be an optical member. Examples of optical members include: lenses such as eyeglasses; front protective plates, antireflection plates, polarizing plates, and antiglare plates for displays such as PDP and LCD; for devices such as mobile phones and portable information terminals. Touch panel sheet; disc surface of an optical disc such as a Blu-ray (registered trademark) disc, DVD disc, CD-R, or MO; optical fiber or the like.
　また、本発明によって得られる表面処理層を有する物品は、医療機器または医療材料であってもよい。 Further, the article having the surface treatment layer obtained by the present invention may be a medical device or a medical material.
　表面処理層の厚さは、特に限定されない。光学部材の場合、表面処理層の厚さは、１～５０ｎｍ、好ましくは１～３０ｎｍ、より好ましくは１～１５ｎｍの範囲であることが、光学性能、表面滑り性、摩擦耐久性および防汚性の点から好ましい。 The thickness of the surface treatment layer is not particularly limited. In the case of an optical member, the thickness of the surface treatment layer is in the range of 1 to 50 nm, preferably 1 to 30 nm, more preferably 1 to 15 nm. From the point of view, it is preferable.
　以上、本発明の組成物を使用して得られる物品について詳述した。なお、本発明の組成物の用途、使用方法ないし物品の製造方法などは、上記で例示したものに限定されない。 As mentioned above, the articles obtained using the composition of the present invention have been described in detail. In addition, the use of the composition of this invention, the usage method thru | or the manufacturing method of articles | goods, etc. are not limited to what was illustrated above.
　本発明の組成物について、以下の実施例を通じてより具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、本実施例において、以下に示される化学式はすべて平均組成を示し、パーフルオロポリエーテルを構成する繰り返し単位（ＣＦ２ＣＦ２ＣＦ２Ｏ）の存在順序は任意である。 The composition of the present invention will be described in more detail through the following examples, but the present invention is not limited to these examples. In this example, the chemical formulas shown below all indicate average compositions, and the order of presence of the repeating units (CF 2 CF 2 CF 2 O) constituting the perfluoropolyether is arbitrary.
・合成例１
・パーフルオロポリエーテル変性メチルエステル化合物の合成
　反応器に、メタノール２４０ｇ、トリエチルアミン１９．６ｇを仕込み、窒素気流下、５℃で平均組成ＣＦ３ＣＦ２ＣＦ２Ｏ（ＣＦ２ＣＦ２ＣＦ２Ｏ）３２ＣＦ２ＣＦ２ＣＯＦで表されるパーフルオロポリエーテル変性酸フルオロ化合物５００ｇを滴下し、その後、室温まで昇温させて、撹拌した。続いて、パーフルオロヘキサン３００ｇを加えて撹拌した後、分液ロートに移送し静置後、パーフルオロヘキサン層を分取した。続いて、３規定塩酸水溶液による洗浄操作を行った。次に、パーフルオロヘキサン層に無水硫酸マグネシウム３０ｇを加えて、撹拌した後、不溶物を濾別した。続いて、減圧下で揮発分を留去することにより、末端にメチルエステル基を有する下記のパーフルオロポリエーテル変性メチルエステル体（Ａ）４７６ｇを得た。
・パーフルオロポリエーテル変性メチルエステル化合物（Ａ）：
　　CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CO2CH3 Synthesis example 1
Synthesis of perfluoropolyether-modified methyl ester compound A reactor was charged with 240 g of methanol and 19.6 g of triethylamine, and average composition CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) at 5 ° C. in a nitrogen stream. 500 g of a perfluoropolyether-modified acid fluoro compound represented by 32 CF 2 CF 2 COF was dropped, and then the mixture was heated to room temperature and stirred. Subsequently, after adding 300 g of perfluorohexane and stirring, it was transferred to a separatory funnel and allowed to stand, and then the perfluorohexane layer was collected. Subsequently, a washing operation with a 3N hydrochloric acid aqueous solution was performed. Next, 30 g of anhydrous magnesium sulfate was added to the perfluorohexane layer and stirred, and then the insoluble material was filtered off. Subsequently, volatile components were distilled off under reduced pressure to obtain 476 g of the following perfluoropolyether-modified methyl ester (A) having a methyl ester group at the terminal.
Perfluoropolyether modified methyl ester compound (A):
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CO 2 CH 3
・合成例２
・パーフルオロポリエーテル変性カルボン酸化合物の合成
　反応器に、純水１００ｇ、トリエチルアミン２０．４ｇを仕込み、窒素気流下、５℃で平均組成ＣＦ３ＣＦ２ＣＦ２Ｏ（ＣＦ２ＣＦ２ＣＦ２Ｏ）３２ＣＦ２ＣＦ２ＣＯＦで表されるパーフルオロポリエーテル変性酸フルオロ化合物５００ｇを滴下し、その後、室温まで昇温させて、撹拌した。続いて、パーフルオロヘキサン４００ｇを加えて撹拌した後、分液ロートに移送し静置後、パーフルオロヘキサン層を分取した。続いて、３規定塩酸水溶液による洗浄操作を行った。次に、パーフルオロヘキサン層に無水硫酸マグネシウム３０ｇを加えて、撹拌した後、不溶物を濾別した。続いて、減圧下で揮発分を留去することにより、末端にカルボン酸基を有する下記のパーフルオロポリエーテル変性カルボン酸化合物（Ｂ）４７６ｇを得た。
・パーフルオロポリエーテル変性カルボン酸化合物（Ｂ）：
　　CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CO2H Synthesis example 2
Synthesis of perfluoropolyether-modified carboxylic acid compound 100 g of pure water and 20.4 g of triethylamine were charged into a reactor, and an average composition of CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O at 5 ° C. under a nitrogen stream. ) 500 g of a perfluoropolyether-modified acid fluoro compound represented by 32 CF 2 CF 2 COF was dropped, and then the mixture was heated to room temperature and stirred. Subsequently, 400 g of perfluorohexane was added and stirred, then transferred to a separatory funnel and allowed to stand, and the perfluorohexane layer was collected. Subsequently, a washing operation with a 3N hydrochloric acid aqueous solution was performed. Next, 30 g of anhydrous magnesium sulfate was added to the perfluorohexane layer and stirred, and then the insoluble material was filtered off. Subsequently, volatile components were distilled off under reduced pressure to obtain 476 g of the following perfluoropolyether-modified carboxylic acid compound (B) having a carboxylic acid group at the terminal.
Perfluoropolyether modified carboxylic acid compound (B):
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CO 2 H
・合成例３
・パーフルオロポリエーテル変性リン酸エステル化合物の合成
　反応器に、１，３－ビス（トリフルオロメチル）ベンゼン２００ｇ、塩化ホスホリル５４．５ｇを仕込み、窒素気流下、５℃で平均組成ＣＦ３ＣＦ２ＣＦ２Ｏ（ＣＦ２ＣＦ２ＣＦ２Ｏ）３２ＣＦ２ＣＦ２ＣＨ２ＯＨで表されるパーフルオロポリエーテル変性アルコール化合物２００ｇを滴下し、その後、室温まで昇温させて、撹拌した。続いて、パーフルオロヘキサン４００ｇを加えて撹拌した後、純水を１００ｇ滴下し、撹拌した。その後、分液ロートに移送し静置後、パーフルオロヘキサン層を分取した。続いて、３規定塩酸水溶液による洗浄操作を行った。次に、パーフルオロヘキサン層に無水硫酸マグネシウム１０ｇを加えて、撹拌した後、不溶物を濾別した。続いて、減圧下で揮発分を留去することにより、末端にリン酸基を有する下記のパーフルオロポリエーテル変性リン酸エステル化合物（Ｃ）２０２ｇを得た。
・パーフルオロポリエーテル基含有リン酸エステル化合物（Ｃ）：
　　CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2OP(=O)(OH)2 Synthesis example 3
Synthesis of perfluoropolyether-modified phosphate ester compound A reactor was charged with 200 g of 1,3-bis (trifluoromethyl) benzene and 54.5 g of phosphoryl chloride, and an average composition CF 3 CF 2 at 5 ° C. in a nitrogen stream. 200 g of perfluoropolyether-modified alcohol compound represented by CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OH was dropped, and then the mixture was heated to room temperature and stirred. Subsequently, after adding 400 g of perfluorohexane and stirring, 100 g of pure water was added dropwise and stirred. Thereafter, the perfluorohexane layer was collected after being transferred to a separatory funnel and allowed to stand. Subsequently, a washing operation with a 3N hydrochloric acid aqueous solution was performed. Next, 10 g of anhydrous magnesium sulfate was added to the perfluorohexane layer and stirred, and then the insoluble material was filtered off. Subsequently, volatile matter was distilled off under reduced pressure to obtain 202 g of the following perfluoropolyether-modified phosphate compound (C) having a phosphate group at the terminal.
Perfluoropolyether group-containing phosphate ester compound (C):
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OP (= O) (OH) 2
　実施例１
　上記合成例１で得たパーフルオロポリエーテル変性メチルエステル化合物（Ａ）および下記に示すパーフルオロポリエーテル変性シラン化合物（Ｘ）を、モル比２：９８で混合し、ノベック７２００（スリーエム社製）に溶解させて、濃度２０ｗｔ％になるように、表面処理剤１を調製した。
・パーフルオロポリエーテル変性シラン化合物（Ｘ）
　　CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2OCH2CH2CH2Si(OCH3)3 Example 1
The perfluoropolyether-modified methyl ester compound (A) obtained in Synthesis Example 1 and the perfluoropolyether-modified silane compound (X) shown below are mixed at a molar ratio of 2:98, and Novec 7200 (manufactured by 3M) The surface treating agent 1 was prepared so that it might melt | dissolve in and may be set to 20 wt%.
・ Perfluoropolyether modified silane compound (X)
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 3
　上記で調製した表面処理剤１を化学強化ガラス（コーニング社製、「ゴリラ」ガラス、厚さ０．７ｍｍ）上に真空蒸着した。真空蒸着の処理条件は、圧力３．０×１０－３Ｐａとし、まず、電子線蒸着方式により二酸化ケイ素を７ｎｍの厚さで、この化学強化ガラスの表面に蒸着させて二酸化ケイ素膜を形成し、続いて、化学強化ガラス１枚（５５ｍｍ×１００ｍｍ）あたり、表面処理剤２ｍｇを蒸着させた。その後、蒸着膜付き化学強化ガラスを、温度２０℃および湿度６５％の雰囲気下で２４時間静置した。これにより、蒸着膜が硬化して、表面処理層が形成された。 The surface treating agent 1 prepared above was vacuum-deposited on chemically strengthened glass (Corning, “Gorilla” glass, thickness 0.7 mm). The processing conditions for vacuum deposition were set at a pressure of 3.0 × 10 −3 Pa. First, silicon dioxide was deposited on the surface of this chemically strengthened glass by an electron beam deposition method to a thickness of 7 nm to form a silicon dioxide film. Subsequently, 2 mg of a surface treatment agent was vapor deposited per chemically strengthened glass (55 mm × 100 mm). Thereafter, the chemically strengthened glass with a deposited film was allowed to stand for 24 hours in an atmosphere of a temperature of 20 ° C. and a humidity of 65%. Thereby, a vapor deposition film hardened and a surface treatment layer was formed.
　（実施例２～９）
　パーフルオロポリエーテル変性化合物（Ａ）～（Ｃ）とパーフルオロポリエーテル変性シラン化合物（Ｘ）～（Ｚ）を下記表の組み合わせで、モル比２：９８で混合して表面処理剤を作成した以外は、実施例１と同様にして、表面処理剤を調製し、表面処理層を形成した。
・パーフルオロポリエーテル変性シラン化合物（Ｙ）
　　CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CON(CH3)CH2CH2CH2Si(OCH3)3
・パーフルオロポリエーテル変性シラン化合物（Ｚ）
　　CF3CF2CF2O(CF2CF2CF2O)32CF2CF2CH2OCH2CH2CH2Si[CH2CH2CH2Si(OCH3)3]3 (Examples 2 to 9)
Perfluoropolyether-modified compounds (A) to (C) and perfluoropolyether-modified silane compounds (X) to (Z) were mixed in the following table in a molar ratio of 2:98 to prepare a surface treatment agent. A surface treatment agent was prepared in the same manner as in Example 1 except that a surface treatment layer was formed.
・ Perfluoropolyether modified silane compound (Y)
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CON (CH 3 ) CH 2 CH 2 CH 2 Si (OCH 3 ) 3
・ Perfluoropolyether modified silane compound (Z)
CF 3 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 32 CF 2 CF 2 CH 2 OCH 2 CH 2 CH 2 Si [CH 2 CH 2 CH 2 Si (OCH 3 ) 3 ] 3
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
　比較例１～３
　上記のパーフルオロポリエーテル変性シラン化合物（Ｘ）～（Ｚ）を単独で用いること以外は、実施例１と同様にして、表面処理剤を調製し、表面処理層を形成した。
Figure JPOXMLDOC01-appb-T000042
 Comparative Examples 1 to 3
A surface treatment agent was prepared and a surface treatment layer was formed in the same manner as in Example 1 except that the above perfluoropolyether-modified silane compounds (X) to (Z) were used alone.
Figure JPOXMLDOC01-appb-T000042
　比較例４
　酢酸と上記のパーフルオロポリエーテル変性シラン化合物（Ｘ）をモル比２：９８で混合して表面処理剤を作成した以外は、実施例１と同様にして、表面処理剤を調製し、表面処理層を形成した。 Comparative Example 4
A surface treatment agent was prepared in the same manner as in Example 1 except that acetic acid and the above perfluoropolyether-modified silane compound (X) were mixed at a molar ratio of 2:98 to prepare a surface treatment agent. A layer was formed.
　上記の実施例１～９、比較例１～４にて基材表面に形成された表面処理層について、消しゴム摩擦耐久試験により、摩擦耐久性を評価した。具体的には、表面処理層を形成したサンプル物品を水平配置し、消しゴム（コクヨ株式会社製、ＫＥＳＨＩ－７０、平面寸法１ｃｍ×１．６ｃｍ）を表面処理層の表面に接触させ、その上に５００ｇｆの荷重を付与し、その後、荷重を加えた状態で消しゴムを２０ｍｍ／秒の速度で往復させた。往復回数５００回毎に水の静的接触角（度）を測定した。接触角の測定値が１００度未満となった時点で評価を中止した。最後に接触角が１００度を超えた時の往復回数を、表３に示す。 The friction durability of the surface treatment layers formed on the substrate surface in Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated by an eraser friction durability test. Specifically, a sample article on which a surface treatment layer is formed is placed horizontally, and an eraser (Kokuyo Co., Ltd., KESHI-70, plane size: 1 cm × 1.6 cm) is brought into contact with the surface of the surface treatment layer. A load of 500 gf was applied, and then the eraser was reciprocated at a speed of 20 mm / sec with the load applied. The static contact angle (degree) of water was measured every 500 reciprocations. The evaluation was stopped when the measured value of the contact angle was less than 100 degrees. Finally, Table 3 shows the number of reciprocations when the contact angle exceeds 100 degrees.
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
　上記の結果から、パーフルオロ（ポリ）エーテル基含有シラン化合物およびパーフルオロポリエーテル変性化合物を組み合わせて用いた実施例１～９は、パーフルオロ（ポリ）エーテル基含有シラン化合物を単独で用いた比較例１～３よりも、高い消しゴム耐性を有することが確認された。本発明はいかなる理論によっても拘束されないが、パーフルオロポリエーテル変性化合物（Ａ）～（Ｃ）が、表面処理層作成時に、酸性の触媒として作用し、パーフルオロ（ポリ）エーテル基含有シラン化合物（Ｘ）～（Ｚ）と基材表面との反応性を向上させ、その結果、優れた消しゴム耐久性が得られたと考えられる。また、単に触媒として機能し得る酢酸を用いた比較例４よりも、パーフルオロポリエーテル変性カルボン酸化合物（Ｂ）を用いた実施例４が、高い消しゴム耐性を有することが確認された。本発明はいかなる理論によっても拘束されないが、これは酸がパーフルオロポリエーテル基を有することにより、それ自体が表面処理層の機能に寄与できるためと考えられる。 From the above results, Examples 1 to 9 in which the perfluoro (poly) ether group-containing silane compound and the perfluoropolyether-modified compound were used in combination were compared using the perfluoro (poly) ether group-containing silane compound alone. It was confirmed to have higher eraser resistance than Examples 1 to 3. The present invention is not limited by any theory, but the perfluoropolyether-modified compounds (A) to (C) act as an acidic catalyst when forming the surface treatment layer, and the perfluoro (poly) ether group-containing silane compound ( It is considered that the reactivity between X) to (Z) and the substrate surface was improved, and as a result, excellent eraser durability was obtained. In addition, it was confirmed that Example 4 using the perfluoropolyether-modified carboxylic acid compound (B) has higher eraser resistance than Comparative Example 4 using acetic acid that can simply function as a catalyst. Although this invention is not restrained by any theory, it is thought that this can contribute to the function of the surface treatment layer itself because the acid has a perfluoropolyether group.
　本発明は、種々多様な基材、特に透過性が求められる光学部材の表面に、表面処理層を形成するために好適に利用され得る。 The present invention can be suitably used for forming a surface treatment layer on the surface of a variety of substrates, particularly optical members that require transparency.

Claims (35)

  1. 　下記一般式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）：
    Figure JPOXMLDOC01-appb-C000001
     ［式中：
    　ＰＦＰＥ１は、各出現においてそれぞれ独立して、式：
    　　　－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
    （式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
    で表される基であり；
    　Ｒｆ１は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
    　Ｒ１は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒ２は、各出現においてそれぞれ独立して、水素原子または炭素数１～２２のアルキル基を表し；
    　Ｒ１１は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し；
    　Ｒ１２は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｎ１は、（－ＳｉＲ１ ｎ１Ｒ２ ３－ｎ１）単位毎に独立して、０～３の整数であり；
    　ただし、式（Ａ１）、（Ａ２）、（Ｂ１）および（Ｂ２）において、少なくとも１つのｎ１が、１～３の整数であり；
    　Ｘ１は、それぞれ独立して、単結合または２～１０価の有機基を表し；
    　Ｘ２は、各出現においてそれぞれ独立して、単結合または２価の有機基を表し；
    　ｔは、各出現においてそれぞれ独立して、１～１０の整数であり；
    　αは、それぞれ独立して、１～９の整数であり；
    　α’は、それぞれ独立して、１～９の整数であり；
    　Ｘ５は、それぞれ独立して、単結合または２～１０価の有機基を表し；
    　βは、それぞれ独立して、１～９の整数であり；
    　β’は、それぞれ独立して、１～９の整数であり；
    　Ｘ７は、それぞれ独立して、単結合または２～１０価の有機基を表し；
    　γは、それぞれ独立して、１～９の整数であり；
    　γ’は、それぞれ独立して、１～９の整数であり；
    　Ｒａは、各出現においてそれぞれ独立して、－Ｚ１－ＳｉＲ７１ ｐ１Ｒ７２ ｑ１Ｒ７３ ｒ１を表し；
    　Ｚ１は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
    　Ｒ７１は、各出現においてそれぞれ独立して、Ｒａ’を表し；
    　Ｒａ’は、Ｒａと同意義であり；
    　Ｒａ中、Ｚ１基を介して直鎖状に連結されるＳｉは最大で５個であり；
    　Ｒ７２は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒ７３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｐ１は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｑ１は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｒ１は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、式（Ｃ１）および（Ｃ２）において、少なくとも１つのｑ１が１～３の整数であり；
    　Ｒｂは、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒｃは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｋ１は、各出現においてそれぞれ独立して、１～３の整数であり；
    　ｌ１は、各出現においてそれぞれ独立して、０～２の整数であり；
    　ｍ１は、各出現においてそれぞれ独立して、０～２の整数であり；
    　Ｘ９は、それぞれ独立して、単結合または２～１０価の有機基を表し；
    　δは、それぞれ独立して、１～９の整数であり；
    　δ’は、それぞれ独立して、１～９の整数であり；
    　Ｒｄは、各出現においてそれぞれ独立して、－Ｚ２－ＣＲ８１ ｐ２Ｒ８２ ｑ２Ｒ８３ ｒ２を表し；
    　Ｚ２は、各出現においてそれぞれ独立して、酸素原子または２価の有機基を表し；
    　Ｒ８１は、各出現においてそれぞれ独立して、Ｒｄ’を表し；
    　Ｒｄ’は、Ｒｄと同意義であり；
    　Ｒｄ中、Ｚ２基を介して直鎖状に連結されるＣは最大で５個であり；
    　Ｒ８２は、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
    　Ｙは、各出現においてそれぞれ独立して、２価の有機基を表し；
    　Ｒ８５は、各出現においてそれぞれ独立して、水酸基または加水分解可能な基を表し；
    　Ｒ８６は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｎ２は、（－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２）単位毎に独立して、１～３の整数を表し；
    　ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｎ２は１～３の整数であり；
    　Ｒ８３は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｐ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｑ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｒ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　Ｒｅは、各出現においてそれぞれ独立して、－Ｙ－ＳｉＲ８５ ｎ２Ｒ８６ ３－ｎ２を表し；
    　Ｒｆは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し；
    　ｋ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｌ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ｍ２は、各出現においてそれぞれ独立して、０～３の整数であり；
    　ただし、式（Ｄ１）および（Ｄ２）において、少なくとも１つのｑ２は２または３であるか、あるいは、少なくとも１つのｌ２は２または３である。］
    のいずれかで表される少なくとも１種のパーフルオロ（ポリ）エーテル基含有シラン化合物、および
    　下記式（Ｅ１）：
    Figure JPOXMLDOC01-appb-C000002
     ［式中：
    　ＰＦＰＥ２は、各出現においてそれぞれ独立して、式：
    　　　－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－
    （式中、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。）
    で表される基であり；
    　Ｒｆ２は、各出現においてそれぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
    　Ｚ２は、単結合または２価の有機基を表し；
    　ｘは１または２であり；
    　ｘが１である場合、Ａは、－ＣＯＯＲ３、－ＰＯ（ＯＲ３）２、－ＳＯ２（ＯＲ３）、または－ＳＯ（ＯＲ３）であり；
    　ｘが２である場合、Ａは、－ＰＯ（ＯＲ３）－であり；
    　Ｒ３は、水素原子または炭化水素基である。］
    で表される少なくとも１種の化合物
    を含む組成物。     The following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
    Figure JPOXMLDOC01-appb-C000001
     [Where:
    PFPE 1 has the formula:
    - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
    (Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of existence of each repeating unit with a, b, c, d, e or f and parenthesized is arbitrary in the formula.)
    A group represented by:
    Rf 1 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
    R 1 represents, independently at each occurrence, a hydroxyl group or a hydrolyzable group;
    R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
    R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
    R 12 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    n1 is an integer of 0 to 3, independently for each (—SiR 1 n1 R 2 3-n1 ) unit;
    Provided that in formulas (A1), (A2), (B1) and (B2), at least one n1 is an integer of 1 to 3;
    Each X 1 independently represents a single bond or a divalent to 10-valent organic group;
    X 2 represents each independently a single bond or a divalent organic group at each occurrence;
    t is independently an integer from 1 to 10 at each occurrence;
    each α is independently an integer from 1 to 9;
    α ′ is each independently an integer of 1 to 9;
    Each X 5 independently represents a single bond or a divalent to 10-valent organic group;
    each β is independently an integer from 1 to 9;
    each β ′ is independently an integer from 1 to 9;
    X 7 each independently represents a single bond or a divalent to 10-valent organic group;
    each γ is independently an integer from 1 to 9;
    each γ ′ is independently an integer from 1 to 9;
    R a independently represents at each occurrence —Z 1 —SiR 71 p1 R 72 q1 R 73 r1 ;
    Z 1 represents, independently at each occurrence, an oxygen atom or a divalent organic group;
    R 71 independently represents R a ′ at each occurrence;
    R a ′ is synonymous with R a ;
    In R a , the maximum number of Si linked in a straight chain via the Z 1 group is 5;
    R 72 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
    R 73 independently represents at each occurrence a hydrogen atom or a lower alkyl group;
    p1 is independently an integer from 0 to 3 at each occurrence;
    q1 is independently an integer from 0 to 3 at each occurrence;
    r1 is independently an integer from 0 to 3 at each occurrence;
    Provided that in formulas (C1) and (C2), at least one q1 is an integer of 1 to 3;
    R b independently represents a hydroxyl group or a hydrolyzable group at each occurrence;
    R c independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    k1 is independently an integer of 1 to 3 at each occurrence;
    l1 is independently an integer from 0 to 2 at each occurrence;
    m1 is independently an integer from 0 to 2 at each occurrence;
    X 9 each independently represents a single bond or a divalent to 10-valent organic group;
    each δ is independently an integer from 1 to 9;
    each δ ′ is independently an integer from 1 to 9;
    R d independently represents at each occurrence —Z 2 —CR 81 p2 R 82 q2 R 83 r2 ;
    Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence;
    R 81 independently represents R d ′ at each occurrence;
    R d ′ is synonymous with R d ;
    In R d , the maximum number of C linked in a straight chain via the Z 2 group is 5;
    R 82 independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
    Y represents a divalent organic group independently at each occurrence;
    R 85 independently represents at each occurrence a hydroxyl group or a hydrolyzable group;
    R 86 independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    n2 represents an integer of 1 to 3 independently for each (-Y-SiR 85 n2 R 86 3-n2 ) unit;
    Provided that in formulas (D1) and (D2), at least one n2 is an integer of 1 to 3;
    R 83 each independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    p2 is independently an integer from 0 to 3 at each occurrence;
    q2 is independently an integer from 0 to 3 at each occurrence;
    r2 is independently an integer from 0 to 3 at each occurrence;
    R e independently represents at each occurrence —Y—SiR 85 n2 R 86 3-n2 ;
    R f independently represents a hydrogen atom or a lower alkyl group at each occurrence;
    k2 is independently an integer from 0 to 3 at each occurrence;
    l2 is independently an integer from 0 to 3 at each occurrence;
    m2 is an integer from 0 to 3 independently at each occurrence;
    However, in the formulas (D1) and (D2), at least one q2 is 2 or 3, or at least one l2 is 2 or 3. ]
    At least one perfluoro (poly) ether group-containing silane compound represented by any one of the following formula (E1):
    Figure JPOXMLDOC01-appb-C000002
     [Where:
    PFPE 2 has the formula:
    - (OC 6 F 12) a - (OC 5 F 10) b - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f -
    (Wherein, a, b, c, d, e and f are each independently an integer of 0 to 200, and the sum of a, b, c, d, e and f is at least 1, The order of existence of each repeating unit with a, b, c, d, e or f and parenthesized is arbitrary in the formula.)
    A group represented by:
    Rf 2 represents, independently at each occurrence, an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
    Z 2 represents a single bond or a divalent organic group;
    x is 1 or 2;
    when x is 1, A is —COOR 3 , —PO (OR 3 ) 2 , —SO 2 (OR 3 ), or —SO (OR 3 );
    when x is 2, A is —PO (OR 3 ) —;
    R 3 is a hydrogen atom or a hydrocarbon group. ]
    A composition comprising at least one compound represented by:
  2. 　Ｒｆ１が、炭素数１～１６のパーフルオロアルキル基である、請求項１に記載の組成物。 The composition according to claim 1, wherein Rf 1 is a perfluoroalkyl group having 1 to 16 carbon atoms.
  3. 　ＰＦＰＥ１が下記式（ａ）、（ｂ）または（ｃ）：
    　　－（ＯＣ３Ｆ６）ｄ－　　（ａ）
    ［式中、ｄは１以上２００以下の整数である。］
    　　－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－　　（ｂ）
    ［式中、ｃおよびｄは、それぞれ独立して、０以上３０以下の整数であり；
    　ｅおよびｆは、それぞれ独立して、１以上２００以下の整数であり；
    　ｃ、ｄ、ｅおよびｆの和は、１０以上２００以下の整数であり；
    　添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
    　　－（Ｒ６－Ｒ７）ｑ－　　（ｃ）
    ［式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり；
    　Ｒ７は、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から選択される２または３つの基の組み合わせであり； 
    　ｑは、２～１００の整数である。］
    である、請求項１または２に記載の組成物。     PFPE 1 is represented by the following formula (a), (b) or (c):
    -(OC 3 F 6 ) d- (a)
    [Wherein, d is an integer of 1 or more and 200 or less. ]
    - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
    [Wherein, c and d are each independently an integer of 0 to 30;
    e and f are each independently an integer of 1 to 200;
    the sum of c, d, e and f is an integer from 10 to 200;
    The order of existence of each repeating unit with parentheses c, d, e or f and enclosed in parentheses is arbitrary in the formula. ]
    -(R 6 -R 7 ) q- (c)
    [Wherein R 6 is OCF 2 or OC 2 F 4 ;
    R 7 is a group selected from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or a combination of 2 or 3 groups selected from these groups ;
    q is an integer of 2 to 100. ]
    The composition according to claim 1 or 2, wherein
  4. 　Ｘ１、Ｘ５、Ｘ７およびＸ９が２価の有機基であり、α、β、γおよびδが１であり、α’、β’、γ’およびδ’が１である、請求項１～３のいずれか１項に記載の組成物。 X 1 , X 5 , X 7 and X 9 are divalent organic groups, α, β, γ and δ are 1, and α ′, β ′, γ ′ and δ ′ are 1. 4. The composition according to any one of 1 to 3.
  5. 　Ｘ１、Ｘ５、Ｘ７およびＸ９が、それぞれ独立して、－（Ｒ３１）ｐ’－（Ｘａ）ｑ’－
    ［式中：
    　Ｒ３１は、それぞれ独立して、単結合、－（ＣＨ２）ｓ’－（式中、ｓ’は、１～２０の整数である）またはｏ－、ｍ－もしくはｐ－フェニレン基を表し；
    　Ｘａは、－（Ｘｂ）ｌ’－（式中、ｌ’は、１～１０の整数である）を表し；
    　Ｘｂは、各出現においてそれぞれ独立して、－Ｏ－、－Ｓ－、ｏ－、ｍ－もしくはｐ－フェニレン基、－Ｃ（Ｏ）Ｏ－、－Ｓｉ（Ｒ３３）２－、－（Ｓｉ（Ｒ３３）２Ｏ）ｍ’－Ｓｉ（Ｒ３３）２－（式中、ｍ’は１～１００の整数である）、－ＣＯＮＲ３４－、－Ｏ－ＣＯＮＲ３４－、－ＮＲ３４－および－（ＣＨ２）ｎ’－（式中、ｎ’は１～２０の整数である）からなる群から選択される基を表し；
    　Ｒ３３は、各出現においてそれぞれ独立して、フェニル基、Ｃ１－６アルキル基またはＣ１－６アルコキシ基を表し；
    　Ｒ３４は、各出現においてそれぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基を表し；
    　ｐ’は、０、１または２であり；
    　ｑ’は、０または１であり；
    　ここに、ｐ’およびｑ’の少なくとも一方は１であり、ｐ’またはｑ’を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり；
    　Ｒ３１およびＸａは、フッ素原子、Ｃ１－３アルキル基およびＣ１－３フルオロアルキル基から選択される１個またはそれ以上の置換基により置換されていてもよい。］
    で表される基である、請求項１～４のいずれか１項に記載の組成物。     X 1 , X 5 , X 7 and X 9 are each independently-(R 31 ) p ' -(X a ) q'-
    [Where:
    Each of R 31 independently represents a single bond, — (CH 2 ) s ′ — (wherein s ′ is an integer of 1 to 20) or o-, m- or p-phenylene group;
    X a represents — (X b ) l ′ — (wherein l ′ is an integer of 1 to 10);
    X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (wherein m ′ is an integer of 1 to 100), —CONR 34 —, —O—CONR 34 —, —NR 34 — And represents a group selected from the group consisting of — (CH 2 ) n ′ — (wherein n ′ is an integer of 1 to 20);
    R 33 independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group at each occurrence;
    R 34 independently represents at each occurrence a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
    p ′ is 0, 1 or 2;
    q ′ is 0 or 1;
    Wherein at least one of p ′ and q ′ is 1, and the order of presence of each repeating unit in parentheses with p ′ or q ′ is arbitrary in the formula;
    R 31 and X a may be substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. ]
    The composition according to any one of claims 1 to 4, which is a group represented by:
  6. 　Ｘ１、Ｘ５、Ｘ７およびＸ９が、それぞれ独立して：
    単結合、
    －ＣＨ２Ｏ（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３－、
    －ＣＨ２Ｏ（ＣＨ２）６－、
    －ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２－、
    －ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＦ２ＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２－、
    －ＣＨ２ＯＣＨ２ＣＨＦＣＦ２ＯＣＦ（ＣＦ３）ＣＦ２ＯＣＦ２ＣＦ２ＣＦ２－
    －ＣＨ２ＯＣＦ２ＣＨＦＯＣＦ２ＣＦ２ＣＦ２－Ｃ（Ｏ）ＮＨ－ＣＨ２－、
    －ＣＨ２ＯＣＨ２（ＣＨ２）７ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）３－、
    －ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）３－、
    －ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ３）２ＯＳｉ（ＯＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２ＯＣＨ２ＣＨ２ＣＨ２Ｓｉ（ＯＣＨ２ＣＨ３）２ＯＳｉ（ＯＣＨ２ＣＨ３）２（ＣＨ２）２－、
    －ＣＨ２－、
    －（ＣＨ２）２－、
    －（ＣＨ２）３－、
    －（ＣＨ２）４－、
    －（ＣＨ２）５－、
    －（ＣＨ２）６－、
    －ＣＯ－
    －ＣＯＮＨ－
    －ＣＯＮＨ－ＣＨ２－、
    －ＣＯＮＨ－（ＣＨ２）２－、
    －（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－
    －ＣＯＮＨ－（ＣＨ２）３－、
    －ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
    －ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、
    －ＣＯＮＨ－（ＣＨ２）６－、
    －ＣＯＮ（ＣＨ３）－（ＣＨ２）６－、
    －ＣＯＮ（Ｐｈ）－（ＣＨ２）６－（式中、Ｐｈはフェニルを意味する）、
    －ＣＯＮＨ－（ＣＨ２）２ＮＨ（ＣＨ２）３－、
    －ＣＯＮＨ－（ＣＨ２）６ＮＨ（ＣＨ２）３－、
    －ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）３－、
    －ＣＨ２Ｏ－ＣＯＮＨ－（ＣＨ２）６－、
    －Ｓ－（ＣＨ２）３－、
    －（ＣＨ２）２Ｓ（ＣＨ２）３－、
    －ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２ＯＳｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）３Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）１０Ｓｉ（ＣＨ３）２（ＣＨ２）２－、
    －ＣＯＮＨ－（ＣＨ２）３Ｓｉ（ＣＨ３）２Ｏ（Ｓｉ（ＣＨ３）２Ｏ）２０Ｓｉ（ＣＨ３）２（ＣＨ２）２－
    －Ｃ（Ｏ）Ｏ－（ＣＨ２）３－、
    －Ｃ（Ｏ）Ｏ－（ＣＨ２）６－、
    －ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－、
    －ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－、
    －ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－（ＣＨ２）３－、
    －ＣＨ２－Ｏ－（ＣＨ２）３－Ｓｉ（ＣＨ３）２－（ＣＨ２）２－Ｓｉ（ＣＨ３）２－ＣＨ（ＣＨ３）－ＣＨ２－、
    －ＯＣＨ２－、
    －Ｏ（ＣＨ２）３－、
    －ＯＣＦＨＣＦ２－、
    Figure JPOXMLDOC01-appb-C000003
     からなる群から選択される、請求項１～５のいずれか１項に記載の組成物。     X 1 , X 5 , X 7 and X 9 are each independently:
    Single bond,
    —CH 2 O (CH 2 ) 2 —,
    —CH 2 O (CH 2 ) 3 —,
    —CH 2 O (CH 2 ) 6 —,
    —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
    -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -,
    -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- ,
    —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
    —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2 —,
    -CH 2 O (CH 2) 3 Si (CH 3) 2 O (Si (CH 3) 2 O) 20 Si (CH 3) 2 (CH 2) 2 -,
    -CH 2 OCF 2 CHFOCF 2- ,
    -CH 2 OCF 2 CHFOCF 2 CF 2- ,
    -CH 2 OCF 2 CHFOCF 2 CF 2 CF 2- ,
    —CH 2 OCH 2 CF 2 CF 2 OCF 2 —,
    —CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 —,
    —CH 2 OCH 2 CF 2 CF 2 OCF 2 CF 2 CF 2 —,
    —CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 —,
    —CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
    —CH 2 OCH 2 CF 2 CF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —,
    -CH 2 OCH 2 CHFCF 2 OCF 2- ,
    -CH 2 OCH 2 CHFCF 2 OCF 2 CF 2- ,
    -CH 2 OCH 2 CHFCF 2 OCF 2 CF 2 CF 2- ,
    —CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 —,
    —CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 —,
    —CH 2 OCH 2 CHFCF 2 OCF (CF 3 ) CF 2 OCF 2 CF 2 CF 2 —
    —CH 2 OCF 2 CHFOCF 2 CF 2 CF 2 —C (O) NH—CH 2 —,
    —CH 2 OCH 2 (CH 2 ) 7 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
    —CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 3 —,
    -CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 3- ,
    —CH 2 OCH 2 CH 2 CH 2 Si (OCH 3 ) 2 OSi (OCH 3 ) 2 (CH 2 ) 2 —,
    -CH 2 OCH 2 CH 2 CH 2 Si (OCH 2 CH 3 ) 2 OSi (OCH 2 CH 3 ) 2 (CH 2 ) 2- ,
    —CH 2 —,
    -(CH 2 ) 2- ,
    -(CH 2 ) 3- ,
    - (CH 2) 4 -,
    -(CH 2 ) 5- ,
    -(CH 2 ) 6- ,
    -CO-
    -CONH-
    -CONH-CH 2- ,
    -CONH- (CH 2 ) 2- ,
    — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —
    -CONH- (CH 2 ) 3- ,
    -CON (CH 3 )-(CH 2 ) 3- ,
    —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl),
    -CONH- (CH 2 ) 6- ,
    -CON (CH 3 )-(CH 2 ) 6- ,
    —CON (Ph) — (CH 2 ) 6 — (wherein Ph represents phenyl),
    —CONH— (CH 2 ) 2 NH (CH 2 ) 3 —,
    —CONH— (CH 2 ) 6 NH (CH 2 ) 3 —,
    —CH 2 O—CONH— (CH 2 ) 3 —,
    —CH 2 O—CONH— (CH 2 ) 6 —,
    -S- (CH 2 ) 3- ,
    -(CH 2 ) 2 S (CH 2 ) 3- ,
    —CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
    —CONH— (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —,
    —CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2 —,
    —CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —,
    -CONH- (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 10 Si (CH 3 ) 2 (CH 2 ) 2- ,
    —CONH— (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 20 Si (CH 3 ) 2 (CH 2 ) 2 —
    -C (O) O- (CH 2 ) 3- ,
    -C (O) O- (CH 2 ) 6- ,
    —CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 2 —,
    —CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —,
    —CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 — (CH 2 ) 3 —,
    —CH 2 —O— (CH 2 ) 3 —Si (CH 3 ) 2 — (CH 2 ) 2 —Si (CH 3 ) 2 —CH (CH 3 ) —CH 2 —,
    -OCH 2- ,
    —O (CH 2 ) 3 —,
    -OCHFCF 2- ,
    Figure JPOXMLDOC01-appb-C000003
     The composition according to any one of claims 1 to 5, which is selected from the group consisting of:
  7. 　ｋ１が３であり、Ｒａ中、ｑ１が３である、請求項１～６のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 6, wherein k1 is 3, and q1 is 3 in Ra .
  8. 　ｌ２が３であり、ｎ２が３である、請求項１～７のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 7, wherein l2 is 3 and n2 is 3.
  9. 　Ｙが、Ｃ１－６アルキレン基、－（ＣＨ２）ｇ’－Ｏ－（ＣＨ２）ｈ’－（式中、ｇ’は０～６の整数であり、ｈ’は０～６の整数である）、または－フェニレン－（ＣＨ２）ｉ’－（式中、ｉ’は、０～６の整数である）である、請求項１～８のいずれか１項に記載の組成物。 Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer of 0 to 6, and h ′ is an integer of 0 to 6) The composition according to any one of claims 1 to 8, which is -phenylene- (CH 2 ) i ' -(wherein i' is an integer of 0 to 6).
  10. 　Ｘ１、Ｘ５、Ｘ７およびＸ９が、それぞれ独立して、３～１０価の有機基である、請求項１～３のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 3, wherein X 1 , X 5 , X 7 and X 9 are each independently a tri- to 10-valent organic group.
  11. 　Ｘ１、Ｘ５、Ｘ７およびＸ９が、それぞれ独立して：
    Figure JPOXMLDOC01-appb-C000004
     ［式中、各基において、Ｔのうち少なくとも１つは、式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）においてＰＦＰＥ１に結合する以下の基：
    －ＣＨ２Ｏ（ＣＨ２）２－、
    －ＣＨ２Ｏ（ＣＨ２）３－、
    －ＣＦ２Ｏ（ＣＨ２）３－、
    －（ＣＨ２）２－、
    －（ＣＨ２）３－、
    －（ＣＨ２）４－、
    －ＣＯＮＨ－（ＣＨ２）３－、
    －ＣＯＮ（ＣＨ３）－（ＣＨ２）３－、
    －ＣＯＮ（Ｐｈ）－（ＣＨ２）３－（式中、Ｐｈはフェニルを意味する）、および
    Figure JPOXMLDOC01-appb-C000005
     であり、
    　別のＴのうち少なくとも１つは、式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）および（Ｄ２）において、炭素原子またはＳｉ原子に結合する－（ＣＨ２）ｎ－（ｎは２～６の整数）であり、残りは、それぞれ独立して、メチル基、フェニル基、炭素数１～６のアルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり、
    　Ｒ４１は、それぞれ独立して、水素原子、フェニル基、炭素数１～６のアルコキシ基または炭素数１～６のアルキル基であり、
    　Ｒ４２は、それぞれ独立して、水素原子、Ｃ１－６のアルキル基またはＣ１－６のアルコキシ基を表す。］
    からなる群から選択される、請求項１０に記載の組成物。     X 1 , X 5 , X 7 and X 9 are each independently:
    Figure JPOXMLDOC01-appb-C000004
     Wherein in each group, at least one of T is PFPE in formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) The following groups bonded to 1 :
    —CH 2 O (CH 2 ) 2 —,
    —CH 2 O (CH 2 ) 3 —,
    —CF 2 O (CH 2 ) 3 —,
    -(CH 2 ) 2- ,
    -(CH 2 ) 3- ,
    - (CH 2) 4 -,
    -CONH- (CH 2 ) 3- ,
    -CON (CH 3 )-(CH 2 ) 3- ,
    —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), and
    Figure JPOXMLDOC01-appb-C000005
     And
    At least one of the other T is a carbon atom or a Si atom in the formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2). — (CH 2 ) n — (n is an integer of 2 to 6) to be bonded, and the rest are each independently a methyl group, a phenyl group, an alkoxy group having 1 to 6 carbon atoms, a radical scavenging group, or an ultraviolet absorption Group,
    Each of R 41 is independently a hydrogen atom, a phenyl group, an alkoxy group having 1 to 6 carbon atoms or an alkyl group having 1 to 6 carbon atoms;
    R 42 each independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group. ]
    11. The composition of claim 10, wherein the composition is selected from the group consisting of:
  12. 　式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）または（Ｄ２）で表されるパーフルオロ（ポリ）エーテル基含有シラン化合物の数平均分子量が、１，０００～３０，０００である、請求項１～１１のいずれか１項に記載の組成物。 Number average molecular weight of perfluoro (poly) ether group-containing silane compound represented by formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The composition according to any one of claims 1 to 11, wherein is from 1,000 to 30,000.
  13. 　パーフルオロ（ポリ）エーテル基含有シラン化合物が、式（Ａ１）および（Ａ２）のいずれかで表される少なくとも１種の化合物である、請求項１～１２のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any one of formulas (A1) and (A2). .
  14. 　パーフルオロ（ポリ）エーテル基含有シラン化合物が、式（Ｂ１）および（Ｂ２）のいずれかで表される少なくとも１種の化合物である、請求項１～１２のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any one of formulas (B1) and (B2). .
  15. 　パーフルオロ（ポリ）エーテル基含有シラン化合物が、式（Ｃ１）および（Ｃ２）のいずれかで表される少なくとも１種の化合物である、請求項１～１２のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any one of formulas (C1) and (C2). .
  16. 　パーフルオロ（ポリ）エーテル基含有シラン化合物が、式（Ｄ１）および（Ｄ２）のいずれかで表される少なくとも１種の化合物である、請求項１～１２のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 12, wherein the perfluoro (poly) ether group-containing silane compound is at least one compound represented by any one of formulas (D1) and (D2). .
  17. 　Ｒｆ２が、炭素数１～１６のパーフルオロアルキル基である、請求項１～１６のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 16, wherein Rf 2 is a perfluoroalkyl group having 1 to 16 carbon atoms.
  18. 　ＰＦＰＥ２が下記式（ａ）、（ｂ）または（ｃ）：
    　　　－（ＯＣ３Ｆ６）ｄ－　　（ａ）
    　［式中、ｄは１以上２００以下の整数である。］
    　　　－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－　　（ｂ）
    　［式中、ｃおよびｄは、それぞれ独立して、０以上３０以下の整数であり；
    　ｅおよびｆは、それぞれ独立して、１以上２００以下の整数であり；
    　ｃ、ｄ、ｅおよびｆの和は、１０以上２００以下の整数であり；
    　添字ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
    　　　－（Ｒ６－Ｒ７）ｑ－　　（ｃ）
    　［式中、Ｒ６は、ＯＣＦ２またはＯＣ２Ｆ４であり；
    　Ｒ７は、ＯＣ３Ｆ６、ＯＣ４Ｆ８、ＯＣ５Ｆ１０およびＯＣ６Ｆ１２から選択される基であるか、あるいは、これらの基から独立して選択される２または３つの基の組み合わせであり；
    　ｑは、２～１００の整数である。］
    である、請求項１～１７のいずれか１項に記載の組成物。     PFPE 2 is represented by the following formula (a), (b) or (c):
    -(OC 3 F 6 ) d- (a)
    [Wherein, d is an integer of 1 or more and 200 or less. ]
    - (OC 4 F 8) c - (OC 3 F 6) d - (OC 2 F 4) e - (OCF 2) f - (b)
    [Wherein, c and d are each independently an integer of 0 to 30;
    e and f are each independently an integer of 1 to 200;
    the sum of c, d, e and f is an integer from 10 to 200;
    The order of existence of each repeating unit with parentheses c, d, e or f and enclosed in parentheses is arbitrary in the formula. ]
    -(R 6 -R 7 ) q- (c)
    [Wherein R 6 is OCF 2 or OC 2 F 4 ;
    R 7 is a group selected from OC 3 F 6 , OC 4 F 8 , OC 5 F 10 and OC 6 F 12 , or 2 or 3 groups independently selected from these groups A combination;
    q is an integer of 2 to 100. ]
    The composition according to any one of claims 1 to 17, which is
  19. 　Ｚ２における２価の有機基が、
    －（ＣＲ１８ ２）ｋ７－（Ｏ）ｋ８－（ＮＲ１９）ｋ９－、
    ［式中：
    　Ｒ１８は、それぞれ独立して、水素原子またはフッ素原子であり；
    　Ｒ１９は、それぞれ独立して、水素原子、フェニル基またはＣ１－６アルキル基を表し；
    　ｋ７は、１～２０の整数であり；
    　ｋ８は、０～１０の整数であり；
    　ｋ９は、０～１０の整数であり；
    　ここに、ｋ７、ｋ８またはｋ９を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
    である、請求項１～１８のいずれか１項に記載の組成物。     The divalent organic group in Z 2 is
    -(CR 18 2 ) k7- (O) k8- (NR 19 ) k9- ,
    [Where:
    Each R 18 is independently a hydrogen atom or a fluorine atom;
    R 19 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group;
    k7 is an integer from 1 to 20;
    k8 is an integer from 0 to 10;
    k9 is an integer from 0 to 10;
    Here, k7, k8 or k9 is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ]
    The composition according to any one of claims 1 to 18, which is
  20. 　Ｚ２が、－（ＣＦ２）ｋ７’－または－（ＣＦ２）ｋ７’－（Ｏ）ｋ８’－
    ［式中：
    　ｋ７’は、１～６の整数であり；
    　ｋ８’は、１～３の整数であり；
    　ここに、ｋ７’またはｋ８’を付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。］
    である、請求項１～１８のいずれか１項に記載の組成物。     Z 2 is — (CF 2 ) k7 ′ — or — (CF 2 ) k7 ′ — (O) k8 ′ —
    [Where:
    k7 ′ is an integer from 1 to 6;
    k8 ′ is an integer from 1 to 3;
    Here, k7 ′ or k8 ′ is attached in parentheses and the order of existence of each repeating unit is arbitrary in the formula. ]
    The composition according to any one of claims 1 to 18, which is
  21. 　Ａが、－ＣＯＯＲ３である、請求項１～２０のいずれか１項に記載の組成物。 A is -COOR 3, A composition according to any one of claims 1 to 20.
  22. 　式（Ｅ１）で表される化合物の数平均分子量が、１，０００～３０，０００である、請求項１～２１のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 21, wherein the compound represented by the formula (E1) has a number average molecular weight of 1,000 to 30,000.
  23. 　式（Ａ１）、（Ａ２）、（Ｂ１）、（Ｂ２）、（Ｃ１）、（Ｃ２）、（Ｄ１）または（Ｄ２）で表されるパーフルオロ（ポリ）エーテル基含有シラン化合物の数平均分子量と、式（Ｅ１）で表される化合物の数平均分子量の差が２０００以内である、請求項１～２１のいずれか１項に記載の組成物。 Number average molecular weight of perfluoro (poly) ether group-containing silane compound represented by formula (A1), (A2), (B1), (B2), (C1), (C2), (D1) or (D2) The composition according to any one of claims 1 to 21, wherein the difference between the number average molecular weight of the compound represented by formula (E1) is 2,000 or less.
  24. 　含フッ素オイル、シリコーンオイル、および触媒から選択される１種またはそれ以上の他の成分をさらに含有する、請求項１～２３のいずれかに記載の組成物。 The composition according to any one of claims 1 to 23, further comprising one or more other components selected from fluorine-containing oils, silicone oils, and catalysts.
  25. 　含フッ素オイルが、式（３）：
    Ｒｆ３－（ＯＣ４Ｆ８）ａ１－（ＯＣ３Ｆ６）ｂ１－（ＯＣ２Ｆ４）ｃ１－（ＯＣＦ２）ｄ１－Ｒｆ４　　　　　　　　　　　　　　　（３）
    ［式中：
    　Ｒｆ３は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
    　Ｒｆ４は、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基、フッ素原子または水素原子を表し；
    　ａ１、ｂ１、ｃ１およびｄ１は、ポリマーの主骨格を構成するパーフルオロ（ポリ）エーテルの４種の繰り返し単位数をそれぞれ表し、互いに独立して０以上３００以下の整数であって、ａ１、ｂ１、ｃ１およびｄ１の和は少なくとも１であり、添字ａ１、ｂ１、ｃ１またはｄ１を付して括弧でくくられた各繰り返し単位の存在順序は、式中において任意である。］
    で表される１種またはそれ以上の化合物である、請求項２４に記載の組成物。     The fluorine-containing oil has the formula (3):
    Rf 3- (OC 4 F 8 ) a1- (OC 3 F 6 ) b1- (OC 2 F 4 ) c1- (OCF 2 ) d1 -Rf 4 (3)
    [Where:
    Rf 3 represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
    Rf 4 represents an alkyl group having 1 to 16 carbon atoms, a fluorine atom or a hydrogen atom which may be substituted with one or more fluorine atoms;
    a1, b1, c1 and d1 each represent the number of four types of repeating units of perfluoro (poly) ether constituting the main skeleton of the polymer, each independently an integer of 0 to 300, , C1 and d1 are at least 1, and the order of presence of each repeating unit in parentheses with the suffix a1, b1, c1 or d1 is arbitrary in the formula. ]
    25. The composition of claim 24, wherein the composition is one or more compounds represented by:
  26. 　さらに溶媒を含む、請求項１～２５のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 25, further comprising a solvent.
  27. 　表面処理剤である、請求項１～２６のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 26, which is a surface treatment agent.
  28. 　防汚性コーティング剤または防水性コーティング剤として使用される、請求項１～２７のいずれか１項に記載の組成物。 The composition according to any one of claims 1 to 27, which is used as an antifouling coating agent or a waterproof coating agent.
  29. 　請求項１～２８のいずれか１項に記載の組成物を含有するペレット。 A pellet containing the composition according to any one of claims 1 to 28.
  30. 　基材と、該基材の表面に、請求項１～２８のいずれか１項に記載の組成物より形成された層とを含む物品。 An article comprising a substrate and a layer formed from the composition according to any one of claims 1 to 28 on a surface of the substrate.
  31. 　基材がガラスである、請求項３０に記載の物品。 The article according to claim 30, wherein the substrate is glass.
  32. 　基材がサファイアガラス、ソーダライムガラス、アルカリアルミノケイ酸塩ガラス、ホウ珪酸ガラス、無アルカリガラス、クリスタルガラスおよび石英ガラスから成る群から選択されるガラスである、請求項３０に記載の物品。 The article according to claim 30, wherein the substrate is a glass selected from the group consisting of sapphire glass, soda lime glass, alkali aluminosilicate glass, borosilicate glass, alkali-free glass, crystal glass and quartz glass.
  33. 　光学部材である、請求項３０～３２のいずれか１項に記載の物品。 The article according to any one of claims 30 to 32, which is an optical member.
  34. 　ディスプレイである、請求項３０～３３のいずれか１項に記載の物品。 The article according to any one of claims 30 to 33, which is a display.
  35. 　下記式（Ｅ１）：
    Figure JPOXMLDOC01-appb-C000006
     ［式中：
    　Ｒｆ２は、それぞれ独立して、１個またはそれ以上のフッ素原子により置換されていてもよい炭素数１～１６のアルキル基を表し；
    　ＰＦＰＥ２は、それぞれ独立して、－（ＯＣ６Ｆ１２）ａ－（ＯＣ５Ｆ１０）ｂ－（ＯＣ４Ｆ８）ｃ－（ＯＣ３Ｆ６）ｄ－（ＯＣ２Ｆ４）ｅ－（ＯＣＦ２）ｆ－を表し、ここに、ａ、ｂ、ｃ、ｄ、ｅおよびｆは、それぞれ独立して０以上２００以下の整数であって、ａ、ｂ、ｃ、ｄ、ｅおよびｆの和は少なくとも１であり、ａ、ｂ、ｃ、ｄ、ｅまたはｆを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意であり；
    　Ｚ２は、単結合または２価の有機基を表し；
    　ｘは１または２であり；
    　ｘが１である場合、Ａは、－ＣＯＯＲ３、－ＰＯ（ＯＲ３）２、－ＳＯ２（ＯＲ３）、または－ＳＯ（ＯＲ３）であり；
    　ｘが２である場合、Ａは、－ＰＯ（ＯＲ３）－であり；
    　Ｒ３は、水素原子または炭化水素基である。］
    で表される少なくとも１種の化合物を含む、パーフルオロ（ポリ）エーテル基含有シラン化合物の縮合促進剤。     Following formula (E1):
    Figure JPOXMLDOC01-appb-C000006
     [Where:
    Each Rf 2 independently represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms;
    Each of PFPE 2 is independently-(OC 6 F 12 ) a- (OC 5 F 10 ) b- (OC 4 F 8 ) c- (OC 3 F 6 ) d- (OC 2 F 4 ) e- (OCF 2) f - represents, here, a, b, c, d, e and f is an independently zero or greater than 200 integer, a, b, c, d, e and f Is at least 1, and the order of presence of each repeating unit in parentheses with a, b, c, d, e or f is arbitrary in the formula;
    Z 2 represents a single bond or a divalent organic group;
    x is 1 or 2;
    when x is 1, A is —COOR 3 , —PO (OR 3 ) 2 , —SO 2 (OR 3 ), or —SO (OR 3 );
    when x is 2, A is —PO (OR 3 ) —;
    R 3 is a hydrogen atom or a hydrocarbon group. ]
    A perfluoro (poly) ether group-containing silane compound condensation accelerator comprising at least one compound represented by the formula:
PCT/JP2017/031171 2016-09-08 2017-08-30 Composition containing perfluoro(poly)ether group-containing silane compound WO2018047695A1 (en)

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